AMERICAN CERAMIC SOCIETY bulletin emerging ceramics & glass technology Molten-core fabrication of novel optical fibers MAY 2013 T Commercial Yb:SiO2 fiber Yb: YAG-derived all-glass fiber Wound healing borate glass fibers • Computational methods for concrete • Young Professionals Network • PACRIM/GOMD program guide . ACers Corporate Membership Join today to receive up to $2,000 in value! Small Corporations 50 employees or less Two individual memberships (valued at $240) Annual Dues = $325 Large Corporations 51 employees or more Six individual memberships (valued at $720) Annual Dues = $1,000 The American Ceramic Society www.ceramics.org ACers Corporate Members enjoy these benefits: ACers Bulletin: • Spotlight listing during first month of membership • Two corporate member appreciation ads throughout the year Special pricing on electronic and print advertising ceramicSOURCE: • Priority ranking for your company in search results • Company logo displayed in print and electronic directory • Premium placement in electronic and print editions noting corporate membership Recognition: • InFocus member newsletter listing during first month of membership • Use of ACerS corporate member logo on your website and collateral materials • Corporate member appreciation signs at ACerS technical meetings · Eligibility for ACerS Corporate Achievement Awards • $200 discount on booth space at ACerS ICACC exhibition ceramics.org. • One sidebar ad on a landing page of your choice for 30 days at no charge, excluding homepage • One \"featured\" job posting on the Online Career Center for 30 days at no charge • • Landing page that includes description, logo and company-specific information of your choice • Inclusion in ACerS corporate member roster www.ceramics.org/corporate Contact Tricia Freshour at 614-794-5827 or tfreshour@ceramics.org to learn more! contents feature articles May 2013 • Vol. 92 No. 4 Molten-core fabrication of novel optical fibers. Stephanie Morris and John Ballato 24 The molten-core approach allows simple fabrication of novel optical fibers—for use in high-energy lasers, telecommunication devices, and sensors—in long lengths from not-so-novel crystalline and amorphous materials.. Wound healing: An update on Mo-Sci\'s novel borate glass fibers Peter Wray 30 Wray updates on Mo-Sci\'s progress since he first reported on their wound healing borate glass fibers two years ago. Clinical trials show that the fibers promote healing by providing raw materials the body uses to rebuild tissue. Structural study of Na₂O-FеO-Fе2O3-P2º¸ glasses by high-pressure liquid chromatography and Raman spectroscopy cover story optical fibers. Molten-core fabrication of novel 36 Lina Ma and Richard K. Brow GOMD Kreidl Lecture award winner Lina Ma\'s extended abstract summarizes her PhD work studying phosphate glass structure. (Credits: Background image: Ryan Durdle, ITG, Beckman Institute; Inset images: P. Dragic; UIUC) - page 24 The computational materials science of concrete: Past, present and future. 40 Edward J. Garboczi Computational materials science of concrete is now a viable discipline that bridges the gap between fundamental principles and practical applications. meetings PACRIM 10, including GOMD 2013 Short courses Schedule of events Hotel information, optional tours Plenary speakers. Award lectures Symposia schedule. UNITECR 2013 46 47 47 47 Wound healing: An update on Mo-Sci\'s novel borate glass fibers 48 (Credit: ACerS) 48 - page 30 49 52 Technical program 52 Keynote and plenary speakers. 53 Schedule at a glance, short courses. 53 Exhibitors, optional tours. . 54 12th International Conference on Ceramic Processing Science (ICCPS-12) 55 Schedule, technical program 55 Plenary speakers 55 Hotel information 55 4th Advances in Cement-Based Materials: Characterization, Processing, Modeling, and Sensing 56 advances in Della Roy lecture, symposia information 56 Hotel information 56 Highlights from the St. Louis Section/RCD and 49th Annual Symposium on Refractories 40 57 nanomaterials Commercialization of carbon nanotubes and their surprisingly long history (Credit: Wikimedia) - page 20 American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 1 AMERICAN CERAMIC SOCIETY Obulletin contents May 2013 • Vol. 92 No. 4 Editorial and Production Eileen De Guire, Editor ph: 614-794-5828 fx: 614-794-5815 edeguire@ceramics.org Peter Wray, Contributing Editor Russell Jordan, Contributing Editor Tess M. Speakman, Graphic Designer Editorial Advisory Board Olivia Graeve, Chair, Alfred University Allen Apblett, Oklahoma State University Andrew Gyekenyesi, Ohio Aerospace Institute Joe Ryan, Pacific Northwest National Laboratory Rafael Salomão, University of São Paulo Finn Giuliani, Imperial College London Eileen De Guire, Staff Liaison, The American Ceramic Society Customer Service/Circulation ph: 866-721-3322 fx: 240-396-5637 customerservice@ceramics.org Advertising Sales National Sales Patricia A. Janeway, Associate Publisher pjaneway@ceramics.org ph: 614-794-5826 fx: 614-794-5822 Europe Richard Rozelaar media@alaincharles.com ph: 44-(0)-20-7834-7676 fx: 44-(0)-20-7973-0076 Executive Staff Charles G. Spahr, Executive Director and Publisher cspahr@ceramics.org Sue LaBute, Human Resources Manager & Exec. Assistant slabute@ceramics.org Megan Bricker, Dir. Marketing & Membership Services mbricker@ceramics.org Mark Mecklenborg, Dir. Technical Publications & Meetings mmecklenborg@ceramics.org Linda Ballinger, Director of Finance and Operations Iballinger@ceramics.org Officers Richard Brow, President David Green, President-elect George Wicks, Past President Ted Day Treasurer Charles Spahr, Executive Director Board of Directors Keith Bowman, Director 2012-2015 Elizabeth Dickey, Director 2012-2015 William Fahrenholtz, Director 2009-2013 Vijay Jain, Director 2011-2014 William Lee, Director 2010-2013 Ivar Reimanis, Director 2011-2014 Lora Cooper Rothen, Director 2011-2014 Robert Schwartz, Director 2010-2013 Mrityunjay (Jay) Singh, Director 2012-2015 David Johnson Jr., Parliamentarian Address 600 North Cleveland Avenue, Suite 210 Westerville, OH 43082-6920 The American Ceramic Society www.ceramics.org departments News & Trends 3 Argentina sets ambitious science investment target, brain-drain reversal agenda • ARPA-E\'s online \'university\' continues to expand offerings • • China defends rare-earth stance: Smuggling exceeding legal exports • Freedonia: World refractory demand to grow annually 3.4 percent through 2016 Acers Spotlight • Welcome to our newest Corporate Member! • Computational Design of Ceramic Materials-First TIG to kick off at PACRIM Engineering Ceramics Division opens nominations for awards • Nominations open for GOMD Cooper Scholar Award • • GOMD lecture awards Ceramics in Energy • 14 Amorphous mixed-metal oxide process opens electrolysis catalyst opportunities Graphene on vanadium oxide \'ribbons\' shows promise for lithium-ion battery cathodes Research Briefs 16 • Role of hydrogen bonds in extremely flexible vanadium oxide nanofiber paper • There\'s more to multifunctional ultra-flyweight aerogel produced at a Zhejiang U. lab Advances in Nanomaterials 20 Commercialization of carbon nanotubes and their surprisingly long history Ceramics in the Environment Biofuels byproduct shown to be effective cement supplement • • • MIT Concrete Hub updates work on sustainability research columns Book Review Richard K. Brow Review of \'The Constitution of Glass\' Deciphering Ye Xiang Computational simulation of structure and diffusion in bioactive glass resources Calendar.. Classified Advertising Display Advertising Index Corrections to the April ACerS Bulletin The MAX phases micrograph used on the cover was taken by Liangfa Hu, TAMU. 21 21 58 64 4 59 60 63 6630 American Ceramic Society Bulletin covers news and activities of the Society and its members, includes items of interest to the ceramics community and provides the most current information concerning all aspects of ceramic technology, including R&D, manufacturing, engineering and marketing. American Ceramic Society Bulletin (ISSN No. 0002-7812). ©2013. Printed in the United States of America. ACerS Bulletin is published monthly, except for February, July and November, as a “dual-media\" magazine in print and electronic format (www.ceramicbulletin.org). Editorial and Subscription Offices: 600 North Cleveland Avenue, Suite 210, Westerville, OH 43082-6920. Subscription included with American Ceramic Society membership. Nonmember print subscription rates, including online access: United States and Canada, 1 year $95; international, 1 year $150.* Rates include shipping charges. International Remail Service is standard outside of the United States and Canada. *International nonmembers also may elect to receive an electronic-only, e-mail delivery subscription for $75. Single issues, January-November: member $6.00 per issue; nonmember $7.50 per issue. December issue (ceramicSOURCE): member $20, nonmember $25. Postage/handling for single issues: United States and Canada, $3 per item; United States and Canada Expedited (UPS 2nd day air), $8 per item; International Standard, $6 per item. POSTMASTER: Please send address changes to American Ceramic Society Bulletin, 600 North Cleveland Avenue, Suite 210, Westerville, OH 43082-6920. Periodical postage paid at Westerville, Ohio, and additional mailing offices. Allow six weeks for address changes. ACSBA7, Vol. 92, No. 4, pp 1-64. All feature articles are covered in Current Contents. 2 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 news & trends ARPA-E\'s online \'university\' continues to expand offerings One free resource for people in the materials field that may grow in significance is the nearly year-old ARPA-E \"University.\" The university concept grew out of ARPA-E\'s 2012 Innovation Summit held in the spring. It is basically a collection of live and recorded webinar presentations. The first offering was posted in May 2012, and since then the agency has been been ramping up the content. Although the sessions are being organized with ARPA-E teams in mind, the learning opportunity is open to anyone. For example, on April 3rd the university offered the first installment of what is being promised as a free \"Office Hours\" series. Participants can interact in a live Q&A with an ARPA-E program director on a particular technical topic. This first Office Hours featured ARPAE\'s Ilan Gur and focused on the agency\'s AMPED (Advanced Management and Protection of Energy Storage Devices) program. The goal of AMPED is to \"reduce the cost, volume, and weight of electrified vehicle battery systems by as much as 20-50 percent while retaining or improving lifetime, safety, and performance.\" Advanced registration is required to participate in office hours events. ARPA-E University also has archived materials from its Technology-to-Market series through the university portal. Presentations include • Technology-to-Market Licensing 101; Preparing and Conducting Effective Negotiation; • . Energy Innovation and IP Strategy; Materials from these sessions, and, in some cases, recordings of the webinars are available at no charge. Visit www.arpa-e.gov Experts DTA and TGA analysis can help predict drying and firing behavior of raw materials. arpa.e Customized Sankey diagrams visually highlight heat inputs and losses in dryers and kilns. Technical Consulting on process energy conservation and product quality is a growing service at Harrop. Each year, dozens of customers engage us for technical analysis and unbiased advice on kiln energy use and drying and firing problems. • • Here\'s what we offer: Complete process energy audits to measure thermal efficiency and recommend both operational and capital improvements Diagnosis and solutions to product quality problems • The largest, most qualified Tech Services staff of any kiln manufacturer in the U.S. • In-house 10,000 sq. ft. testing lab and pilot plant for precise characterization of raw materials and development of optimized drying and firing cycles. For expert help, look no further than Harrop. Visit www.harropusa.com, or call us at 614-231-3621 to discuss your special requirements. • Winning Technical Pitches; • Telling Your Story: Successful The Scientific Method for Getting Presentation Techniques; Technology to Market; and • Demystifying Money: The Many Sources of Capital. American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org HARROP INDUSTRIES, INC.. Fire our imagination 3 news & trends Argentina sets ambitious science investment target, brain-drain reversal agenda Some people in the United States pay far too little attention and give far too little credit to what goes on in Central and South America. If they had, they would have seen a report that the Argentine government proposed a new national science strategy, a plan called \"Innovative Argentina 2020.\" The new plan sets some huge and admirable goals: 4 Business news Leco to manufacture accredited reference materials under guidelines of A2LA accreditation program (www.leco.com)... PPG introduces new moderately reflective, emerald green glass with spectral selectivity in any climate zone (www.ppg. com)...Kyocera announces enhanced, unified display division (www.global. kyocera.com)...Northern Frac Proppants signs sand supply agreement with Carbo Ceramics (www.nfproppants.com). Thermo-Calc Software releases new version of its computational thermodynamics software (www.thermocalc.com)... Cabot extends Dow Corning relationship with capacity expansion in Europe (www. investor.cabot-corp.com)...Orbite Aluminae Inc. and Veolia Environmental Services create partnership to recycle and remediate red mud from alumina production (www.orbitealuminae.com)... Reco2, a new answer to energy saving from Sacmi (www.ceramicworldweb. it)...Morgan Technical Ceramics launches new high-performance piezoelectric material (www.morgantechnicalceramics. com)...Osram LEDs, halogen Eco bulb lights up the Aidastella cruise ship (www. osram.com)...PANalytical launches new XRF analysis software (www.panalytical. com)...Morgan Thermal Ceramics offers Cerox fired refractory shapes and engineering expertise (www.morganthermal ceramics.com)... Fraunhofer IKTS partand • Triple the investment in science; Double the number of researchers; • Convince Argentine researchers who have settled elsewhere to return to their homeland. The time frame for the first two goals is seven years. Unfortunately, neither a roadmap nor the funding sources for expanding the National System of Science, Technology and Innovation is available at this time. Moreover, the repatriation issue is a touchy one. According to the news ners with Mayur Renergy Solutions Inc. to develop SOFC systems for the Indian market (www.ikts.fraunhofer.de)...H.C. Starck achieves successful fiscal year 2012 despite considerable economic slowdown (www.hcstarck.com)...Obama reiterates plan to use oil revenue for alternative energy R&D (www.ogj.com)...AGC invests in Triton Microtechnologies\' viafill technology (www.agc.com)...Bosch announces SOFC field tests for home CHP to start in 2014 (www.bosch-presse. de)…….Global pigments market is expected to reach USD 14.7 billion in terms of revenue and 4.4 million tons in terms of volume by 2018 (www.transparency marketresearch.com)...Alta Devices achieves 30.8% efficiency record with new generation solar cell technology (www.altadevices.com)... North America advanced structural ceramics market to hit $4.4B by 2016, with bioceramics leading the way (www.companiesandmarkets. com)... Global cement demand to see +4.9% growth (www.khl.com)...CerameUnie strengthens its expertise with three new team members (www.cerameunie. eu)...U.S. Silica posts record earnings and revenue for the quarter and the year; revenue increased 50% in 2012 (www.phx. corporate-ir.net)... Schott\'s wood stove design challenge to promote clean burning (www.us.schott.com) report, Lino Barañao, the government\'s science and technology minister, asked rhetorically while presenting the plan, which of the nations great resources were the most poorly managed? He said that most people would suggest the answer is oil. Barañao said the right answer is \"even more embarrassing—it is the brains of Argentine scientists.\" He went on to say that, in essence, Argentina generously gave free brainpower, and the ability it has to generate prosperity, to the northern hemisphere, and because education in Argentina is free, this means there was \"a clear net transfer of resources.\" The factors considered when an Argentine scientist or engineer is making a decision about whether to stay or leave are not clear. However, there was a time under an adverse political and military situation in Argentina when people with or pursuing degrees were persona non grata. They often were among the \"disappeared.\" Indeed, Barañao, himself, noted there was a time when researchers were \"considered dangerous, or at least expendable, \'because the technology was coming from outside\".\" Lack of respect may be another problem. Barañao explained that because of the lack of support, scientists believe, \"We do not ask anything [of Argentina], but do not ask anything of us.” In these circumstances some distance themselves from a society they consider not sufficiently appreciative. There seem to be other cultural issues as well. Barañao spoke of strengthening the system that involves more collaboration and that science universities and companies must pull in the same direction, so that citizens receive something substanwww.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 tive in return for their taxes. There is reticence among all the parties, in which the scientist sees the entrepreneur as a selfish entity thinking only of profit, and the employer sees the researcher as a parasite that drains but never produces anything but sterile knowledge. Barañao said these ideas are false and must be banished by all sides. The story reports that investment in science and technology in 2002 was about 0.44 percent of GDP. The new plan will increase funding from the current 0.65 percent of GDP to 1.65 percent in 2020. The author of the story notes that not every Argentine leader has a firm grip on science and reports that President Cristina Fernandez bumbled her role in announcing the plan by asserting, for example, that “diabetes is a disease of affluent people\" and that Argentine Amaranth also has some essential amino acids \"that we do not have.\" Of course, Argentina does not have a lock on the stockpile of politicians who are clueless about S&T. China defends rare-earth stance: Smuggling exceeding legal exports During the recent European Raw Materials Conference, China\'s Zhang Lirong reiterated his nation\'s position that despite WTO actions, restrictions, which his country has been placing on rare-earth-related exports, are largely the result of concerns about the environmental effects of mining and refining these materials. According to a report from EurActiv.com, Zhang, China\'s deputy ambassador to the European Union, asserted that the conflict over rare-earths pits the European Union and the United States against \"environmental standards we have adopted. ... The measures we have taken are a part of the growing awareness of the need for environmental protection and sustainable production.\" As part of its reporting on this story, EurActiv.com noted that Chinese officials have argued that better controls over mining and production of minerals and metals was essential to address worsening environmental and health conditions that have fueled public anger. A DELTECH, INC. American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org Recently, Beijing announced it would take steps to tackle urban air pollution that has choked the capital and other cities this winter. Zhang apparently made his comments WE BUILD THE FURNACE TO FIT YOUR NEED® Sustained Operating Temperatures up to 2000°C www.deltechfurnaces.com 5 news & trends Satellite photo of China\'s Bayan Obo Mining District. as a reflection upon a WTO ruling jointly brought by the EU and the US against China for creating blocks to supplying the two groups with needed strategic materials, such as bauxite, coke, magnesium, manganese, and zinc. Although the complaint and the subsequent ruling did not explicitly address rare-earths, the WTO action was seen as a proxy for a full battle over access to Chinese elements and ores. Although the Great Recession temporarily has turned down the heated dialogue about Chinese rare-earths exports (and demand for exports actually was well below the nation\'s export ceiling for 2012), Zhang pledged at the meeting, \"China will continue to supply the world market.\" But Zhang also said China, “calls on other suppliers of raw materials to share their materials.\" This probably means that, in the long run, countries with domestic rare earth deposits-but not the gumption to deal with the mess that comes with processing the ores-ought to rethink their position. No one seems to dispute China\'s assertions, viz., that the negative effects of rare-earth mining are far from being contained. On the contrary, the situation may be growing worse because China\'s regulatory structure, so far, is apparently losing the battle to stop bootleg mines and rare-earth smuggling. For example, a 2012 China Daily news report, headlined \"Smuggling blights rare-earths industry,\" revealed that the amount of smuggled rare-earth 6 Credit: NASA; Wikipedia.) products exceeds that which is legally traded. The smug gling of mineral resources out of China, especially rare-earths, continues to increase, a senior official from the General Administration of Customs said. The minerals are smuggled mainly to neighboring countries, such as Japan and the Republic of Korea, Chen Jianxin, deputy director of the administration\'s antismuggling bureau, recently told China Daily. Chen says the huge demand from foreign markets and China\'s high customs duties for rare-earths are the main reasons behind the rise in smuggling. He declined to disclose the latest statistics on the smuggling, but China\'s first white paper on the rare-earths industry, released by the State Council in June, paints a grim picture. The report said that in 2011, the amount of rare-earths smuggled out of China was 20 percent higher than the amount of products that legally left the country. According to customs, China exported about 18,600 tons of rareearths products in 2011, accounting for 61 percent of the rare-earths export quota of 30,184 metric tons released by the Ministry of Commerce for 2011. At the same time, more than 21,000 tons were smuggled out, according to the report. Of the estimated 21,000 tons, only eight cases involving 769 tons of the minerals were detected as part of a campaign to crack down on rare-earths smuggling, according to customs. China has some real problems that cannot be overlooked by the rest of the world. One would hope that the US and Europe will stick with initiatives to develop domestic rare-earth production capabilities, increase recycling and reuse, and spur research to find substitutes and alternatives, such as are being investigated at the new Critical Materials Hub (Ames Laboratory, Ames, Iowa) and the European Innovation Partnership on Raw Materials (Brussels, Belgium). Adding up—NAMII announces first additive manufacturing R&D awards The National Additive Manufacturing Innovation Institute (NAMII) Youngtown, Ohio in March announced its first $4.5 million in awards for seven projects. Matching funds from proposal winners bring the value of the awards up to $5 million. The Obama administration established NAMII in August 2012 as the pilot institute for the National Network for Manufacturing Innovation (NNMI). President Obama brought the Youngstown-based institute to the nation\'s attention when he mentioned it in January\'s State of the Union address. The public-private-academic consortium comprises 40 companies, nine research universities, five community colleges, and 11 nonprofits. (Obama announced the NNMI concept just one year ago, in March 2012, and provided it with $45 million in federal funding from DOD, DOE, Department of Commerce, NSF, and NASA.) According to the NAMII press release, all seven winning projects come from the ranks of NAMII consortium members and are R&D projects that address aspects of NAMII\'s four thrust areas: technology development; technology transition; additive manufacturing enterprise; and education/ workforce outreach. According to the press release, none of these projects specify research on ceramic materials. The focus seems to be on polymers and metals. NAMII says it will announce its second call for proposals in June at the RAPID 2013 Conference and Exposition in Pittsburgh, Pa. Hopefully, it will add ceramic materials to the mix. ACerS\'s www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 often has reported in CTT that additive manufacturing is an excellent fabrication technology for ceramics. The press release announced the following awards. • \"Maturation of Fused Depositing Modeling (FDM) Component Manufacturing\" Rapid Prototype + Manufacturing LLC (RP+M) • \"Qualification of Additive Manufacturing Processes and Procedures for Repurposing and Rejuvenation of Tooling\" Case Western Reserve University • \"Sparse-Build Rapid Tooling by Fused Depositing Modeling (FDM) for Composite Manufacturing and Hydroforming\" Missouri University of Science and Technology • \"Fused Depositing Modeling (FDM) for Complex Composites Tooling\" Northrop Grumman Aerospace Systems • \"Maturation of High-Temperature Selective Laser Sintering (SLS) Technologies and Infrastructure\" Northrop Grumman Aerospace Systems • “Thermal Imaging for Process Monitoring and Control of Additive Manufacturing\" Pennsylvania State University Center for Innovative Materials Processing through Direct Digital Deposition (CIMP 3D) \"Rapid Qualification Methods for Powder Bed Direct Metal Additive Manufacturing Processes\" Case Western Reserve University Visit www.namii.org. Where are the ceramics? We are pleased to see NAMII make seven significant additive manufacturing R&D awards, but it appears that they are all for polymers or metals. (Credit: LBL.) It\'s A Matter Of Choice ED CM Furnaces, long recognized as an industrial leader in performance-proven, high temperature fully continuous sintering furnaces for MIM, CIM and traditional press and sinter now OFFERS YOU A CHOICE, for maximum productivity and elimination of costly down time. Choose one of our exclusive BATCH hydrogen atmosphere Rapid Temp furnaces. Designed for both debinding and sintering, these new furnaces assure economical, simple and efficient operation. OR... choose our continuous high temperature sintering furnaces with complete automation and low hydrogen consumption. E-Mail: info@cmfurnaces.com Web Site: http://www.cmfurnaces.com CONTACT US for more information on our full line of furnaces with your choice of size, automation, atmosphere capabilities and temperature ranges up to 3100°F / 1700°C. CM FURNACES INC. 103 Dewey Street Bloomfield, NJ 07003-4237 Tel: 973-338-6500 Fax: 973-338-1625 American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 7 8 news & trends Freedonia: World refractory demand to grow annually 3.4 percent through 2016 The Freedonia Group issued a new report about the market for refractory materials, \"Refractories to 2016,\" and, generally speaking, the outlook is good worldwide, including the view on North America and Western Europe, where refractory demand has ebbed and flowed quite a bit over the past decade. Freedonia predicts an average global growth rate of 3.4 percent per annum to 46.3 million metric tons. The outlook for revenue is even better, with Freedonia predicting that refractory sales will climb 5.3 percent per annum to $46.5 billion in 2016. Freedonia notes that revenue growth is not as strong as gains registered in the 2001-2006 period, something the research group attributes to \"moderation in raw-material costs and refractory prices.\" However, Freedonia also notes that revenues have and will continue to grow faster than tonnage because of the gradual shift in demand from ordinary iron and steel production (now about three-fifths of the demand) to more specialized and longer-lasting applications that can command more premium pricing. The use of more efficient manufacturing methods is another factor. For example, Freedonia points out, \"[Because of] their greater use of more costly, high-quality products, the US, Western Europe, and Japan will account for a somewhat larger share of the world refractory market total in dollar terms (19 percent) in 2016 than they will in tonnage (14 percent).\" Freedonia\'s report also has good news for North, Central, and South America as well as Western Europe. This was welcome information for those attending the combined ACerS St. Louis Section-Refractory Ceramics Division Symposium in St. Louis, Mo. Although Freedonia predicts that tonnage in North America and Western Europe likely will never return to pre2006 levels, the group points out that overall sales will continue to grow for producers, again a reflection of the shift to more specialized refractory items. In the 2011-2016 period, Freedonia predicts that the Asia/Pacific region will post the largest tonnage increases. It will be followed by the Africa/Mideast region, Central and South America, and Eastern Europe. Freedonia, in particular, notes continued strong demand in China, which \"alone will account for more than seven-tenths of all refractory volume gains between 2011 and 2016, because of additional growth in its huge steel, cement, and other heavy manufacturing industries and to the use of less sophisticated production methods in steelmaking and other important markets than those utilized in economically advanced nations, resulting in greater refractory use in per unit of output terms.\" Freedonia also predicts robust growth in tonnage (4.3 percent per annum) for Central and South America for 2016-2021 period, a rate that may surpass Asia. Freedonia analyst Ken Long explains via email, “Market advances in Central and South America will be stimulated by a strong acceleration in steel production growth and supported by a rebound in aluminum output after a period of decline. Brazil, which accounts for the lion\'s share of the region\'s metals production, will the largest refracpost tory sales gains.\" He also writes, \"construction spending in Central and South America will continue to rise nearly as Region Plibrico Co. refractory installation for a biomass gasifier at Eastern Illinois University. quickly from 2016 to 2021 as during the 2011-2016 period, boosting regional consumption and output of cement and flat glass ... helping to offset slower growth in the metal markets.\" Freedonia also reports the relative change in the size of the regional markets between 2001 and 2021. It predicts that the percentage of world shipments in terms of dollar value will have shrunk from 16.6 percent to 6.6 percent for North America and 24.1 percent to 11.1 percent for Western Europe. Visit www.freedonia.com. WORLD REFRACTORIES DEMAND World Refractories Demand North America Western Europe Asia/Pacific Central & South America Eastern Europe Africa/Mideast Demand (thousand metric tons) 2006 2011 2016 Annual growth % 2006- 20112011 2016 35250 39150 46300 2.1 3.4 3465 2695 2855 -4.9 3785 2960 3035 4.8 21470 27150 32900 1650 1675 2070 3090 2660 3015 1.2 0.5 4.8 3.9 0.3 4.3 -3.0 2.5 1790 2010 2425 2.3 3.8 (Credit: Freedonia Group Inc.) www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 (Credit: Plibrico Company.) acers spotlight Welcome to our newest Corporate Member! ACerS recognizes organizations that have joined the Society as Corporate Members. For more information on becoming a Corporate Member, contact Tricia Freshour at tfreshour@ ceramics.org, or visit ACerS special Corporate Member web page, www.ceramics.org/corporate. UCTM Center for Material Sciences Sofia, Bulgaria www.uctm.edu/enversion Computational Design of Ceramic MaterialsFirst TIG to kick off at PACRIM ACerS president, Richard Brow, introduced the idea of \"Technical Interest Groups\" as a way for the Society to interact with scientists and engineers working in cross-cutting fields that include ceramic materials. The first TIG to organize centers on computational approaches to ceramic science and engineering. The group tentatively named itself the \"Computational Design of Ceramic Materials (CDCM) TIG.\" The initiating organizers include Liping Huang of Rensselaer Polytechnic Institute, Veena Tikare of Sandia National Laboratories, and Sujanto Widjaja and Randall Youngman of Corning Inc. The CDCM TIG welcomes members across all divisions within ACerS to promote the integration of computational methods into research programs with experimental and applied components. An informal kick off meeting will be held at PACRIM in June in San Diego, Calif. Watch Ceramic Tech Today for time and place details or contact Huang at huangL5@rpi.edu. Brow would like to have a similar meeting (also at PACRIM) to organize a biomaterials-based TIG. For more information contact Brow at brow@mst.edu. Nominations open for GOMD Cooper Scholars Award Note new deadline-May 15, 2013! The Glass and Optical Materials Division invites nominations for the Cooper Scholars Award for undergraduates. The award honors the late Alfred R. Cooper Jr., who was on the faculty at Case Western Reserve University and a prominent MIN-U-SILⓇ AND SIL-CO-SIL® GROUND SILICA When you buy world-class MIN-U-SIL® and SIL-CO-SIL® Ground Silica from U.S. Silica, you can be sure the service you receive is world-class. . U.S. Silica delivers the \"Total Package\" every time: Products tailored to your needs • Convenient packaging choices including bulk and 50, 1000, and 2000# bags • Five convenient mining and processing locations • A dedicated and experienced service team Products produced to the highest standards CALL US TODAY FOR A FREE SAMPLE! 800-345-6170 www.ussilica.com sales@ussilica.com X SILICA American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org acers spotlight contributor to the understanding of many glass phenomena and glass problems. The Cooper Scholars Award is open to undergraduate students who have demonstrated excellence in research and/or project work in glass science or technology. The award recipient will receive an award plaque and a check for $500. The student can be from any country, and membership in The American Ceramic Society, the Glass & Optical Materials Division, or Material Advantage is not required. The winner will present a lecture during the GOMD Cooper Session at MS&T\'13, October 27-31, 2013, in Montreal, Canada. Nomination deadline: May 15, 2013. Contact Kelly Simmons-Potter, GOMD chair, at kspotter@ece.arizona. edu; or Marcia Stout at mstout@ ceramics.org. Website: www.ceramics.org/acerscommunity/award-winners-resources/ alfred-r-cooper-scholars-award | Join new AACS Division free for a year! ACerS recently announced its renamed and revitalized division called the Art, Archaeology, and Conservation Engineering Ceramics Division opens nominations for Mueller, Bridge Building, and Global Young Investigator Awards The Engineering Ceramics Division invites nominations for the James I. Mueller and the Bridge Building Awards. Also, ECD is introducing a new Global Young Investigator Award for 2014. The Mueller Award honors the enormous contributions of James I. Mueller to the ECD and to the field of engineering ceramics and recognizes the accomplishments of individuals who have made similar contributions. The main selection criteria are long-term service to ECD and work in the area of engineering ceramics that has significant industrial, national, or academic impact. Award selection can be based on either criterion. The award consists of a memorial plaque, certificate, and an honorarium of $1,000. Visit http:// ceramics.org/acers-community/awardwinners-resources/james-i-muelleraward-and-lecture for more information. The Bridge Building Award recognizes individuals outside of the United States who have made outstanding contributions to engineering ceramics. The main criteria used in selecting the recipient are contributions to the field of engineering ceramics, including expansion of the knowledge base and commercial use thereof, and contributions to the visibility of the field and international advocacy. Award selection can be based on either criterion. The award consists of a plaque, certificate, and an honorarium of $1,000. Visit http://ceramics.org/acers-community/ award-winners-resources/bridge-building-award for more information. The Global Young Investigator Award recognizes an outstanding scientist, anywhere in the world, who is conducting research in academia, in industry, or at a government-funded laboratory. Candidates must be ACerS members and must be 35 years of age or younger. Selection of the awardee will be based on the nomination and accompanying evidence of scientific contributions and visibility of the field, and advocacy of the global young investigator and professional scientific forum. The award consists of $1,000 and a certificate. Nomination deadline for all three awards: July 15, 2013. Contact: Sujanto Widjaja at widjajas@corning.com. Website: www.ceramics.org/acerscommunity/award-winners-resources Science (AACS) Division, formerly known as the Art Division (See ACerS Bulletin, April 2013). AACS aims to advance the scientific understanding of materials in ceramic and glass art and to provide information regarding its preservation, creation, and interpretation. In 2013, AACS plans to participate in the ACerS Annual Meeting in October, arrange an informative tutorial, add valuable resources to the webpage, and get the word out about AACS. Lynnette Madsen of the National Science Foundation, Marc Walton of the Getty Conservation Institute, Glenn Gates of the Walters Art Museum, and Katherine Faber of Northwestern University make up the Executive Committee. Does it sound interesting and like something you want to be involved in? If yes, you are invited to join AACS at no charge-free-for a year! To take advantage of this offer, contact Marcia Stout at mstout@ceramics. org. She will add AACS to your ACerS membership at no charge. (The offer to add AACS to your ACerS membership is valid through the end of 2013.) After the first year, division dues are $10 per division if you select more than one. One division affiliation automatically comes with your ACerS membership at no charge. Website: www.ceramics.org/ divisions/aacs GOMD lecture awards The Glass and Optical Materials Division announces its 2013 award recipients. Awards (with one exception) will be presented at the June 2013 GOMD Annual Meeting in San Diego, Calif., which will be held in conjunction with PACRIM 10. Stephen Elliott, one of the two 2013 Morey Award winners, will accept his award and deliver his lecture at GOMD 2014 in Aachen, Germany. See the program guide beginning on p. 46 for full GOMD program details. 10 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 Stookey Lecture of Discovery Thursday, June 6, 8:00-8:50 a.m. Shay G. Clinton Shay, retired, Corning Inc. The torturous path of the fusion sheet process development In the 1950s and 1960s, Corning developed a revolutionary process to produce pristine flat glass without polishing. This was called \"fusion,\" and it evolved as an alternative to the widely used Pilkington float process. Shay led the team that invented and developed fusion and its applicability to chemically strengthened, Pyrex, ophthalmic, and LCD products. However, despite significant technical advancement and personal sacrifice on their part for 35 years, the fusion developers retired or passed away without seeing commercial success. In the late 1990s, the convergence of the emerging needs for LCD television and fusion\'s thin, low warp, hard-glass came into alignment. Fusion is used today to produce a majority of the glass for liquid-crystal displays as well as Corning\'s Gorilla Glass protective cover glasses used in smartphones, tablets, and electronic products. Today, at 91 years old, Shay continues to champion fusion and is active in defining many new technology directions under investigation today. Shay will share the story of fusion process development-how the team overcame many challenges and, with Corning\'s management support, eventually developed a world-changing glassforming process. His message has special relevance for today-where the expense and risk of process research has caused most to shy away from its pursuit. George W. Morey Award Tuesday, June 4, 8:00-8:50 a.m. Krol Denise Krol, University of California, Davis Focus and Flash! Changing the structure of glass with light Focused femtosecond lasers can alter the structure of transparent materials, such as glass, with submicrometer resolution and high spatial precision. This technique offers a unique manufacturing tool for the fabrication of complex three-dimensional structures embedded inside glass, as opposed to conventional patterning and lithography techniques that are typically restricted to surface layers. In this talk Krol will review the basic principles of ultrafast laser modification of glass and highlight some recent work in this area with an American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org Developers of Specialty Glass and Custom Ceramics • Hybrids • Discrete Components . Overglazes • Thick Film Pastes • Solar Metallization Pastes • Dielectric & Conductive Paste Additives • Standard & Custom LTCC Formulations • Bioactive Glass Applications • Calcined Mixtures ceradyne, inc. VIOX The right glass makes all the difference. VIOX.COM 11 acers spotlight emphasis on the role of glass composi tion and structure. Denise M. Krol is a professor at the University of California, Davis, in the Department of Chemical Engineering and Materials Science. She earned a PhD in mathematics and physical sciences from Utrecht University, the Netherlands. Prior to her appointment at UC Davis, she was a physicist at Lawrence Livermore National Lab, visiting professor at Stanford University, member of the technical staff at AT&T Bell Labs, and a research scientist at Philips Research Labs. She currently divides her time between UC Davis and Utrecht University, where she is a visiting professor in the Physics Department. Krol holds five patents and has published more than 130 journal articles. She is a Fellow of The American Ceramic Society, Fellow of the Optical Society of America and NSF-Visiting Professorships for Women award winner. Her research investigates optical materials, nonlinear optics, and nanophotonics with a current emphasis on ultrafast laser structuring of glass. Stephen Elliott Elliott Elliott will deliver his Morey Lecture at GOMD 2014 in Aachen, Germany. The title will be announced later. Stephen Elliott is a professor of chemical physics at Cambridge University and a Fellow of the Trinity College, Cambridge, UK. He has published more than 300 papers in glass science, such as structure and modeling of amorphous solids, vibrational states of disordered solids, electronic structure of glasses, amorphous chalcogenides, and phase change materials. He authored or coauthored three textbooks: Physics of Amorphous Materials, The Physics and Chemistry of Solids, and Vibrations in Disordered Solids. Norbert J. Kreidl Award for Young Scholars Tuesday, June 4, 1:00-1:50 p.m. Lina Ma, Missouri University of Science and Technology Structural study of Na₂O-FeO-Fe2O3P₂O, glasses by highpressure liquid chromatography and Raman Μα spectroscopy Ma is a fourth-year PhD ceramic engineering candidate studying under the supervision of Richard Brow, Curators\' Professor of Materials Science and Engineering at the Missouri University of Science and Technology. She earned BS and MS degrees in materials science and engineering from Tongji University in Shanghai, China. Ma expects to defend her thesis later this year. See p. 36 for an extended abstract of her work. Education Integration Committee Young Professionals Network-A young person\'s entré to the Society Sehirlioglu By Alp Sehirlioglu, YPN Cochair Many ACerS members have heard about the Young Professionals Network (YPN), but who exactly is this group? What do we do? The YPN of ACerS is an incredible array of talented, well-educated, and innovative individuals less than 40 years old or within their first 10 years of professional employment. We represent a wide crosssection of research, academia, and industry from all over the world, but, this group is relatively new to ACerS. Here\'s our story. The YPN was formed in 2009 by Megan Bricker, Membership Director for the Society. For the next couple of years, the YPN existed as a loosely organized group of members who were early in their careers and searching for greater networking and engagement opportunities through the Society. In 2012, we asked to be formally recognized by the ACerS Board of Directors and collaborated to move forward in a more organized, meaningful manner. At its July 2012 meeting, the board changed the bylaws to allow for \"self directed\" committees such as the YPN. This new structure allows committees to welcome anybody who is looking for ways to volunteer and contribute to the Society in general, without running an election or seeking approval from the board. The Society strongly encourages the involvement of young professionals and actively supports new awards, sponsors gatherings, and has been increasing the visibility of young professionals in the Society. The committee works with other ACerS committees to inform them of YPN activities, as well as to find ways to work together. Since its inception less than a year ago, our group has created opportunities for young professionals to Education Integration Committee Subcommittees CEC reps EIC Chair Representatives Keramos (Pres.) PCSA (Chair) NICE reps Staff Liaison YPN SAC reps 12 At-Large (Optional) www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 meet each other and to meet the members of the Society at large. Examples include gatherings at the Future Leaders Program in Chicago (ICC4), MS&T\'12 in Pittsburgh, EMA 2013 in Orlando, and ICACC\'13 in Daytona. The MS&T\'12 YPN event included young professionals from other societies such as TMS and ASM International to increase interaction between our organizations. In addition, a new myacers.ceramics.org discussion board and virtual meeting space provides an easy-to-access forum where a young professional can join the YPN and be an active participant. Some activities and opportunities for YPN members are . • • • Networking and social receptions at ACerS conferences; Eligibility to apply for the Du-Co Ceramics Young Professional Award; Programming; Writing for publications and newsletters; Opportunities to organize meetings at a high level; • Society recognition and atten• dance at invitation-only workshops (e.g., ACerS Future Leaders Program); Volunteer opportunities with committees and divisions; Membership drives; • • Increased web presence; is involved in will accelerate your career and you will be joining a strong support network that is banding together to change the ceramics and glass world. Who can join? The YPN membership open to any member who is in their first 10 years of professional experience or under 40 years old. Domestic and international members are welcome in the group, and anyone can participate through physical or virtual gatherings. The Society strongly encourages all to become involved. To join the YPN and take advantage of its network and the volunteer opportunities, contact myself at alp.sehirlioglu@case.edu or ACerS Membership Director, Megan Bricker at mbricker@ ceramics.org. CERAMIC TECH TODAY Flexible vanadium oxide paper. (Credit: Burghard; Wiley.) Get daily updates and biweekly emails on breaking news. Recently we reported on • • • SOFC and energy strategy Commercializing carbon nanotubes Additive manufacturing Optical properties of (oxy) nitrides ARPA-E university www.ceramics.org/ceramictechtoday Don\'t leave the scale up of your new material to chance. • Make lifelong friends in your \"career home;\" and much more. How can you get involved? If you are a \"seasoned\" member of ACers, reach out to our committee with ideas or help to make a stronger connection with new members in the Society. For example, offer to talk at a YPN event, volunteer to introduce new members to your colleagues at meetings, or maybe just send a quick email \"welcome to the Society\" message. For all young professionals who are not part of ACerS YPN yet, don\'t wait! Get involved now. The connections you make and the activities you can get Thermal Process Engineering, Testing, Design & Systems KHarper Spark the future harperintl.com American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 13 ceramics in energy Amorphous mixed-metal oxide process opens electrolysis catalyst opportunities A paper recently posted on the online Science Express reports that strides have been made in developing a process to use thin amorphous mixed-metal oxide films to deliver an improved catalyst for hydrogen generation via electrolysis (oxygen evolution reaction). The benefits of using crystalline metal oxides, such as IrO, and RuO₂, and mixed-metal oxides as catalysts for large-scale electrolysis are already known. Similar benefits also have been demonstrated with amorphous phases. However, the problem with using the latter has been coming up with a method to produce homogeneous amorphous mixed-metal compositions. Now, researchers from the Department of Chemistry and Centre for Advanced Solar Materials at University of Calgary say they have a low-temperature process, based on photochemical metal-organic deposition (PMOD), that can produce films containing a homogeneous distribution of metal oxides with compositions that can be accurately controlled. The researchers Cross-section Top view are led by Curtis P. Berlinguette, director of the Centre, the goal of which is to conduct inorganic chemistry research aimed at increasing the contribution of solar energy to the global energy mix. There have been other methods to produce amorphous metal oxide catalysts. Electrodeposition techniques exist for this, but their applicability varies widely from metal to metal. Control problems with mixed metals also make it difficult to use electrodeposition to tailor the voltage protocols for catalysts. These are significant problems, because experience has shown that a mixed-metal catalyst is preferable over single-composition catalysts. PMOD is a fairly well-known method that uses an amorphous metal-organic precursor thin film. The film is irradiated under ambient conditions. The resulting photoreaction leads to the formation of metal oxide thin films in the presence of oxygen. In this research, the group used spin coating and PMOD to make homogeneous thin films of amorphous mixed-metal oxides of iron, nickel, and cobalt in various combinations (e.g., α-FeO, α-NiO, α-CoO2, α-FеCoO a-FeNIO, and α-FeCoNiO). The authors report that the catalytic Annealing temperature 100°C film Si substrate 200 nm 200 nm 2 μm 2 μm 600°C film Si substrate preScanning electron micrographs of cross-section and top-down views of FeО films pared by photochemical metal-organic deposition, followed by a one hour annealing step in air at 100 °C (left) and 600°C (right). 14 Credit: University of Calgary.) 100-y-z properties of a-Fe2O3 prepared with their PMOD technique “are superior to hematite, while those of a-Fe, Co Ni O are comparable to noble metal oxide catalysts currently used in commercial electrolyzers.\" Understandably, they are happy with the first generation of these thin films. \"[W]e contend that the PMOD technique opens an entirely new parameter space for discovery and optimization of new heterogeneous electrocatalysts,\" they write. According to a university press release, the professors have patented the technology and set up a spin-off company, FireWater Fuel Corp. FireWater Fuel hopes to have a large scale electrolyzer ready for the commercial market by 2014 and a smaller-scale prototype ready to test for home markets by 2015. The paper is \"Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis\" (doi:10.1126/science.1233638). Graphene on vanadium oxide \'ribbons\' shows promise for lithium-ion battery cathodes Researchers at Rice University are looking at vanadium oxide for lithium battery electrode applications and recently reported on VO2-graphene hybrid ribbons for cathodes. Their work appears in an article in Nano Letters published by the American Chemical Society. The work comes out of Pulickel Ajayan\'s group. Ajayan is a professor in the Mechanical Engineering and Materials Science Department and in the Chemistry Department and is known for his creative thinking about batteries, for example, his work on paintable batteries. According to the paper\'s abstract, although lithium-ion batteries have high energy density, their full potential in applications is not yet realized because \"they lack suitable electrodes capable of rapid charging and discharging to enable a high power density critical for broad applications.\" In a press release, Ajayan says that vanadium oxide has long interwww.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 ((Credit: Ajayan Group/Rice University)) ested the battery research community and that vanadium pentoxide has been used in some Li-ion batteries. However, he points out that oxides generally charge and discharge slowly because their electrical conductivities are low. Ajayan\'s group addressed the slow charge-discharge problem by “baking\" high-conductivity graphene on VO2 ribbons. The graphene forms a weblike coating on the ribbons and serves as a \"speedy conduit for electrons and channels for ions.\" The team reports promising results. Half-cell tests show that the cathodes fully charge and discharge in 20 s and retain 90% of their initial charge capacity even after 1,000 cycles. The team says their best cathode samples were up to 84 wt% “lithium-slurping\" VO2 and held 204 mAh/g of energy. They also appear to be highly stable. The press release reports the \"capacity for lithium storage remained stable after 200 cycles,\" even at high temperatures regimes above 75°C, where the effectiveness of other cathode materials tends to attenuate. The ribbons are made in a simplesounding hydrothermal process, but in the press release, Subin Yang, lead author of the paper, admits, “One challenge to production was controlling the conditions for the cosynthesis of VO₂ ribbons with graphene.\" They make the hybrid ribbons by heating a water suspension of graphene oxide nanosheets and V₂O, powders for hours in an autoclave. The V₂O, reduces completely to VO, and crystallizes into ribbonlike structures that are 10 nm thick, up to 600 nm wide, and tens of micrometers long. Meanwhile, the graphene oxide reduces to graphene and forms a weblike coating on the ribbons. Ajayan thinks this hybrid material could be used in the paintable batteries his team is working on, too. paper, \"BottomFull details are in the up approach toward single-crystalline VO₂-graphene ribbons as cathodes for ultrafast lithium storage,\" Shubin Yang, Yongji Gong, Zheng Liu, Liang Zhan, Graphene-coated ribbons of vanadium oxide, seen in a scanning electron microscope image, show promise as electrode for lithiumion batteries, according to researchers at Rice University. 1μm Daniel P. Hashim, Lulu Ma, Robert Vajtai, and Pulickel M. Ajayan, Nano Letters, DOI: 10.1021/nl400001u. CARBOLITE LABORATORY FURNACES & OVENS • Microwave Assist Furnace to 1600°C . • Box Furnaces to 1800°C • Horizontal & Vertical Tube Furnaces to 1800°C • Top & Bottom Loading Furnaces to 1800°C • Ovens to 600°C • Precise Temperature Control • Superior Temperature Uniformity Tel: 800-543-6208 • Fax: 800-543-6209 sales@carbolite-usa.com • www.carbolite.us CALL FOR OUR NEW CATALOG American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 15 research briefs Role of hydrogen bonds in extremely flexible vanadium oxide nanofiber paper The idea behind biomineralization is to adapt natural processes to synthesize new materials and engineer them into new configurations or engineer new functionalities. A common point of reference is nacre-also called mother of pearl. The organic-inorganic composite secreted by mollusks has a layered structure comprised of platelets of the aragonite form of calcium carbonate held together with mortarlike organic substance, such as chitin or various proteins. The composite structure of brittle platelets bound together by an elastic biopolymer make nacre an exceptionally strong natural material. The aragonite platelets have a characteristic high-aspectratio morphology that helps make the layered structure possible. Paper, too, is made of high-aspectratio constituents, usually fibers. Examples exist that are based on a platelet-biopolymer type of structure (vermiculite, clay, alumina, and some research on carbon nanotube and graphene oxide papers), but few display the characteristics that make paper so useful, especially flexibility. This appears no longer to be the case. A new article from the University of Stuttgart, Germany, reports some fascinating work on “paper” made of vanadium pentoxide nanofibers and its remarkable properties. According to the paper, vanadium pentoxide (V₂O₂) differs from other transition-metal oxides in that it can be synthesized into crystalline nanofibers with extremely high aspect ratios. The group reports making fibers with diameters 1-10 nm and lengths ranging from 100 nm to tens of micrometers. The ribbonlike fibers are made by a polycondensation process in an aqueous solution and are composed of two V₂O5 layers with a layer of water in between. They have a rectangular cross section with oxygen groups and water bonded to the surface, both of which contribute to the bonding between fibers, similar to the role of biopolymer in nacre. The 16 3cm Hydrogen bonding contributes to the extreme flexibility of vanadium pentoxide paper made from high-aspect-ratio nanofibers. paper is made by slow drying vanadia nanofiber sols, which are then floated off the substrate. has The resulting paper is a dark orange color and can be made with a high degree of fiber alignment. The paper extraordinary flexibility and can be bent or rolled. Cylinders can be rolled with diameters as tight as 1 mm. The hydrogen bonds between the fibers led the team to investigate the sensitivity of the papers to water content. They found that drying the paper at 40°C was an important first step, which was followed by an annealing heat treatment at 100°C or 150°C. Without the drying step, the papers cracked. The annealing removes the weakly adsorbed water between the nanofibers. By remov ing it slowly, the fibers are mobile enough to pack tightly, according to the article, \"most likely through the structure-directly capability of the hydrogen bonded between the V₂O, fibers.\" The importance of optimized thermal processing is evident in the tensile strength of the paper. The tensile strength of as-prepared paper is about 76 MPa. After drying, it is about 132 MPa and, after annealing, it pushes toward 200 MPa. The team suggests that the slow drying interlocks the basal planes of the fibers and increases the hydrogenbond density between -OH groups on the surface. The article explains, “The excellent mechanical performance ... can be attributed to the alternating layer structure of the vanadia paper, comprising a stiff inorganic oxide component combined with \'flexible\' layers of water in between, strongly resembling the brick-and-mortar architecture of structure biomaterials like nacre.\" The ordered structure also is reflected in the electrical conductivity. Conductivity increases after drying, and decreases slightly after annealing with the removal of ionic contributions to the overall conductivity. The results also correlated in expected ways with fiber alignment and in-plane and out-of-plane directions. Because of the dramatic flexibility of the paper and its promising properties, especially mechanical, the vanadia paper could be used in a range of applications relating to energy and electronics. The authors suggest a wide range of potential applications, including stretchable electronics, energy storage, flexible electrodes in chemical sensors, actuators, electrochromic devices, batteries, and supercapacitors. They note that the toughness of the paper could reduce the crack formation from swelling that tends to occur during ion intercalation of electrodes, for example. of The article is \"Hydrogen-bond reinforced vanadia nanofiber paper high stiffness,\" by Zaklina Burghard, et al., Advanced Materials, doi: 10.1002/ adma.201300135. www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 (Credit: Burghard; Wiley.) (Credit: Advanced Materials.) There\'s more to multifunctional ultra-flyweight aerogel produced at a Zhejiang U. lab than just \'world\'s lightest material\' record Advanced Materials reports that a research team at Zhejiang University led by Gao Chao has a new ultra-flyweight aerogel (UFA) that might be the world\'s lightest material (0.16 mg/cm³). More important, however, is that this graphene-carbon nanotube (CNT) aerogel is relatively easy to make, appears to be easily scalable, and is moldable into any shape. Moreover, the new UFA is extremely flexible, elastic (independent of temperature), thermally stable, a good electrical conductor, hydrophobic, and capable of absorbing high capacities of organic liquids. The group\'s material is not the first UFA. Within the past 18 months, other researchers have constructed nickel foam with a density of 0.9 mg/cm³ (via electroless plating and subsequently etching away a polymer template). Another group constructed an aerographite with a density of 0.18 mg/cm³ (via a ZnO template-based chemical vapor deposition approach). But, both groups\' dependency on a template also creates enormous limitations to scalability. Sol-gel-derived, low-density aerogels can be made on fairly large scales, but with sol-gel processes it is difficult to control the dimensions of the structures. Gao\'s group, instead, uses a process that involves freezedrying aqueous solutions of CNTs and giant graphene oxide (GGO) sheets, followed by chemical reduction of graphene oxide into graphene using hydrazine vapor. The researchers named their method a \"sol-cryo\" approach and note in their paper that it is easy to make large samples: \"Because of the simplicity of assembly process in our template-free “sol-cryo” methodology and the large-scale availability of GGO and CNTs, the integrated all-carbon aerogels with desired densities and shapes, such as rods, cylinders, papers, and cubes, were readily accessible. More significantly, UFAs can be easily manufactured in a large-scale. For example, a UFA cylinder up to 1,000 cm³ was made with a mold of 1-liter plate.\" A story on the university\'s website reports quotes Gao saying, \"With no need for templates, its size only depends on that of the container. [A] bigger container can help produce the aerogel in bigger size, even to thousands of cubic centimeters or larger.\" The story also reports that Gao believes \"the value of this achievement lies not in the record but in its simple way in developing the material and the superior performance exhibited.\" Briefly speaking, the microstructure of the material is a 3D porous framework constructed with cell walls of randomly oriented, crinkly graphene sheets and CNT \"ribs.” The macrob pores ranged from hundreds of nanometers to tens of micrometers. The authors of the paper say the properties of the UFA derive from the graphene-CNT synergy: “Giant graphene flakes build a framework with macro-pores, making the aerogel ultralight; the coating of CNTs reinforces the relatively flexible graphene substrate and endows their intrinsic elasticity to the coorganized aerogel.\" One of the UFA\'s interesting properties is its elasticity that allows it to be repeatedly compressed and returned to its nearly original size. This sponginess comes in handy in combination with another property: It can rapidly absorb up to 900 times its own weight in oil or other organic liquids. For Starbar and Moly-D elements are made in the U.S.A. with a focus on providing the highest quality heating elements and service to the global market. Over 40 years of service and reliability I Squared R Element Co., Inc. Akron, NY Phone: (716)542-5511 Fax: (716)542-2100 Email: sales@isquaredrelement.com www.isquaredrelement.com American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 17 research briefs example, 1g of UFA can absorb 68.8 of organics g/s. The elasticity remained the same in tests that ranged from [190°C to 300°C. The elasticity also remained after researchers annealed the UFA at 900°C for 5 h. There are probably many ways the elasticity and absorbability can be useful, not the least of which is that, because of its hydrophobicity, it could be a reusable medium to soak oil spills on lakes up and oceans. Gao says in the university story, \"Maybe one day when [an] oil spill occurs, we can scatter them on the sea and absorb the oil quickly. [Because of] its elasticity, both the oil absorbed and the aerogel can be recycled.\" (Another Chinese research group working at Tsinghua and Peking Universities published a paper in 2010 about the use of CNTs for oil spills. Another property of the UFA is that it has elasticity-dependent electrical conductivity. For example, they report connecting an LED lamp to the UFA bulk, and \"its brightness fluctuates upon compressing and releasing the aerogel. This phenomenon promises the application of UFAs as pressure-responsive sensors.\' They also say that by loading the UFA with tiny amounts of certain liquids (say, CCl4 or 1-hexadecanol), they can make conductive composites with very high electrical conductivity compared with just CNT- or graphene-based composites. \" Gao and the other authors also suggest the UFA could find use as supercapacitors and catalyst beds, but another intriguing application they only hint at is its use as a medium that enhances phase-change energy storage materials. For example, unlike other composites, a UFA-paraffin combination delivers higher phase-change enthalpy (AH) than ordinary paraffin. These applications may only be the beginning. When it comes to learning how to leverage the properties of their fluffy stuff, the researchers say their new UFA is \"just like a new-born baby.” A baby that was, perhaps, born with a silver spoon in its mouth. 18 On Mozart\'s music and tuning optical properties of (oxy)nitrides with O/N ratio When Wolfgang Amadeus Mozart was 25 years old he wrote a theme and 12 variations piece called, “Ah, vous dirai-je Maman.\" (The traditional French tune is widely recognized in the English-speaking world as “Twinkle, twinkle little star.\") The simple structure of the melody gave the composer the freedom and structure to explore the music and see how much he could get the melody to give. Joseph DuBose, on classicalconnect.com writes, \"The French tune is stated in simple two-part harmony, allowing ample room for Mozart\'s imagination to run free. Throughout each of the succeeding twelve variations, the harmony is enriched through the introduction of suspensions and chromatic chords. The variations also maintain the tune\'s twenty-four-measure structure. In some, the melody itself is embellished, such as Variations I or III; in others, the tune is set against an embellished countermelody, such as Variation II or VI.\" When you hear the piece (or better yet, watch it), you can almost hear Mozart thinking, \"What happens if I let the left hand show off? What about the right? What if I tiptoe around the melody? How does it sound with both hands pounding and trilling?\" The feature article in the March issue of the Journal of the American Ceramic Society brought this piece of music to mind. The article is a review titled, \"Optical properties of (oxy) nitride materials: A review,\" by RongJun Xie and Hubertus T. Hintzen. The reviewers focus only on the optical properties because, as the authors say in the paper, \"The optical properties of these (oxy)nitrides, in conjunction with their excellent mechanical strength, thermal properties, and chemical stability, enable (oxy)nitrides to be used in a variety of industrial fields....\" Nitrogen is parked between carbon and oxygen on the Periodic Table, so some nitrides have characteristics similar to carbides, while some behave more like oxides. The authors identify two categories of nitrides compounds based on bonding character: transition-metal nitrides and ionic-covalent nitrides. The authors describe the nature of the bonding thus: \"Nitrogen is interstitial in the metal atom arrangement in transition-metal nitrides in which the metal-metal bonds are dominant. On the other hand, nitrogen-(non)metal bonds are common in ionic-covalent nitrides, and (non)metals are interstitial in a nitrogen array.\" This means that transition-metal nitrides have crystal structures and properties that are similar to carbides. Exploring compositions across the transition-metal series of the Periodic Table is like letting the piano left hand show off. Compounds can be refractory (TiN, ZrN, TaN), magnetic (FeN, CON, CrN, MnN), superconducting (NbN, MON, HfN), or catalytic (Ta₂N, TaON, TION). The ionic-covalent family of nitrides behaves more like oxides (see what the right hand can do!). These compounds offer interesting properties, such as ionic conductivity (Li,N), thermomechanical (Si₂N, BN), optoelectronic (GaN, InAlGaN, AIN, BN), and luminescence (α-SiAlON, B-SiALON, M.Si, N., CaAlSiN). The properties of (oxy)nitride compounds change depending on the oxygen-to-nitrogen ratio. The authors say, \"The chemical and physical properties of (oxy)nitrides are greatly connected with the composition of materials, typically the O/N ratio.\" They continue, \"Even at a doping level, the incorporation of nitrogen into an oxidic framework will make changes in the properties.\" This means that optical properties can be tuned in a variety of materials for a wide range of applications, similar to the subtle interplay and balance www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 Credit: Xie, et al.; JACerS; Wiley) between the lower registers and upper registers of the piano keyboard. The review begins with brief definitions of key optical properties: refraction, reflection, absorption, transmission, scattering, and luminescence. In depth consideration is giving for both types of (oxy)nitride compounds to the antireflection and solar selectivity properties of thin films, band gap and absorption edge properties, photoluminescence, and transmittance. As always with ceramics, processing matters, and the authors include process influences along with their discussion on crystal structure and chemical composition. The range of applications for (oxy)nitride materials is vast. Applications for the transition-metal (oxy)nitride group include antireflection coatings; heat mirror coatings for energy efficient architectural windows, aircraft, solar collectors, and lighting; mid- and high-temperature solar absorbers for water heating, space heating and cooling refrigeration, industrial process heat, desalination, solar thermal power systems; and photocatalysis for water splitting, water and atmospheric purification, antifouling, demisting, and deodorizing. An interesting application is as eco-friendly pigments. The colorful transition-metal oxynitride compounds, such as (Ca, La)Ta(O,N)3, could replace heavy-metal-based pigments. Applications for the ionic-covalent (oxy)nitride group includes armor (see, for example, the article on AlON in the March 2013 issue of the ACerS Bulletin); transparent windows, plates, domes, etc.; semiconductor devices; solidstate LED lighting for general illumination, vehicle headlamps, liquid crystal display backlighting; and field-emission displays. When compounded with rare earths, these oxynitrides may find applications as ecological pigments, too. The variations on the theme of optical properties of (oxy) nitride materials appear to be infinite. The paper is \"Optical properties of (oxy)nitride materials: A review,\" by Rong-Jun Xie and Hubertus T. (Bert) Hintzen, JACerS. (doi:10.111/jace/12197). As always, ACerS members have free access to JACerS and ACerS\'s other two journals, the International Journal of Applied Ceramic Technology and the International Journal of Applied Glass Science. Full access, 24/7 is only one membership enrollment away! Ceramic Tech Today blog www.ceramictechtoday.org Online research, papers, policy news, interviews and weekly video presentations ecological pigments phosphors Optical (oxy)nitrides The optical properties of (oxy) nitride materials are tunable by adjusting the oxygen to nitrogen ratio. This opens a broad array of application possibilities. Delivering a perfect refractory is more than our passion. It\'s an Emhart Glass tradition. Partnering for Perfect Packaging Solutions EMHARTGLASS BUCHER CY www.emhartglass.com USA, Owensville, MO +1 (573) 437 2132 American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 19 advances in nanomaterials Commercialization of carbon nanotubes and their surprisingly long history Twenty years is the figure cited in Materials Genome Initiative presentations and documents as the typical time span between new material discovery and commercialization. The MGI aspires to reduce the timeline by half to 10 years. Carbon nanotubes seem to be a good example of a new material that transitioned from discovery to commercialization quickly. CNTs today are used in applications as disparate as Tour de France bicycle frames, antifouling paints, microelectronic interconnects, supercapacitors, water filters, wind turbine blades, nonvolatile random access memory devices, and more. A review article in the Feb. 1, 2013, issue of Science highlights applications for multiwall and single-wall CNTs (MWNT and SWNT, respectively). It also describes manufacturing-scale synthesis and processing methods, economic challenges, and overall outlook for CNT commercialization. According to the article, worldwide CNT production increased by more than a factor of 10 between 2006 and 2011. In 2005, the year that a CNT composite bicycle won the Tour de France, annual global production capacity hovered around 0.2 kilotons. By 2011, global CNT production capacity soared to about 4.6 kilotons per year. (The authors observe that a plethora of press releases promote new applications, but are skimpy on technical details. Production capacity provides a clue to the trajectory of commercialization success.) The article reports that most CNTs produced today are disorganized (unaligned), which limits the ability to capitalize on the interesting properties of aligned structures such as yarns, \"forests,\" and sheets. Nevertheless, there are enough applications for CNTs incorporated into bulk composites and thin films that the authors say CNT powders are \"now entering the growth phase of their product life cycle.\" Chemical vapor deposition is the prevailing manufacturingscale method for synthesizing in production quantities of MWNTs. SWNTs require much closer control of the CVD process, which keeps their prices much higher than MWNTs (by orders of magnitude, according to the article). However, CNTs can still be pricey, themselvesup to about $100 per kilogram, which is as much as 10 times the price of carbon fiber. A multiwall carbon nanotube with triple-wall, \"arm chair\" morphology. Global production capacity of MWNTs is about 4.5 kilotons per year. The article provides a brief overview of applications of CNTs in composite materials, coatings and films, microelectronics, energy storage and environment, and biotechnology. As CNTs progress through their life cycles, manufacturers (and those that regulate their activities) will have to address health and safety standards, disposal and recycling of discards, environmental impact, etc. In addition addressing the producibility of SWNTs, the graphene family of nanoscale carbon materials shows promise for commercial applications ranging from thermal interfaces to aerogel coatings to corrosion prevention coatings. Lessons learned during the transition of CNT technology out of the lab and into the production line should pay dividends for commercializing graphene. So, what about that timeline from discovery to commercialization? Pinpointing the discovery of CNTs is not so easy. In 1991 Japanese physicist, Sumio Iijima, published a paper on CNTs that seems to have been the spark that ignited subsequent intense research and development efforts. Iijima is often credited with being the inventor of CNTs. However, a Wikipedia article (which seems to have done a thorough job tracing the big history of the tiny tubes) traces the 40-year history of CNTs prior to 1991! The first published report of CNTs was in 1952 in a Soviet-era, Russian language journal, and therefore, not noticed. A 1976 article demonstrated vapor phase growth of single walled carbon nanotubes. Other early reports were published in 1979 and 1981. In 1987 the USPTO issued a patent for the production of \"Cylindrically discrete carbon fibrils\" with diameters between 3.5 and 70 nm. Arguably, in 1952, characterization tools, such as transmission electron microscopes, were either rudimentary or did not exist. Probably the same is true for production processes, such as CVD. Consider, too, that even the applications did not exist. The first demonstration of the solid-state transistor, for example, happened in 1947. The point is that the finish line may be easier to define than the starting point. It seems to me that MGI goals should be careful not to dismiss novel materials as \"failures\" even if commercialization takes more than 20 years. 20 20 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 Wikimedia.) Oceramics in the environment Biofuels byproduct shown to be effective cement supplement Researchers at Kansas State University have demonstrated the ability to convert certain bioethanol and other biofuel byproducts into a cementitious material that can replace part of the portland cement used in concrete. The idea is that the waste material could potentially reduce some of the energy requirements and subsequent CO2 production of cement production. Much of the work at KSU has been done by Feraidon Ataie, a doctoral student in civil engineering, who is advised by Kyle Riding, an assistant professor of civil engineering. Ataie\'s research has focused on byproducts from the production of cellulosic ethanol made from agricultural residue, such as wood chips and wheat straw. To be clear, there is a separate process that also produced bioethanol using edible feedstock, such as grains. The byproducts from the grain process can be used as cattle feed. However, the process for agricultural residue that Ataie focused on produces a “high-lignin\" residue (HLR) that has struggled to find a subsequent use. Riding say in a KSU news release, \"Your choices of how to use it are a lot lower. The most common choices would be to either burn it for electricity or dispose of the ash\" in a landfill. The first step to make the material into a usable SCM is to convert it to ash by burning. The agricultural residues ash (ARA) cannot be used directly, and much of Ataie\'s and Riding\'s research has involved looking at how best to convert it to make it as reactive (i.e., accelerating hydration) as possible. Although other researchers already had shown that that dilute acid pretreatment could improve the reactivity of ARA in concrete materials, Ataie went a step further and examined the pozzolanic property of the ARA if acid pretreatment is followed by enzymatic hydrolysis. According to an abstract of some of the duo\'s work, they concluded the following: \"Based on heat of hydration, calcium hydroxide consumption, and compressive strength experiments, it was concluded that the ash produced by burning HLR is a very reactive pozzolanic material that can be used as a partial replacement of cement in concrete materials. Thus, HLRs that are byproducts of biochemical conversion of agricultural residue can be utilized as valuable materials for SCMs production for concrete.\" Indeed, Ataie and Riding found that replacing 20 percent of the cement with cellulosic SCM increased the compressive strength of the concrete by 32 percent. \"The utilization of this byproduct is important in both concrete materials and biofuel production,\" Ataie says in the release. \"If you use this in concrete to increase strength and quality, then you add value to this byproduct rather than just landfilling it. If you add value to this byproduct, then it is a positive factor for the industry. It can help to reduce the cost of bioethanol production.\" in Kansas STAVE Cification of High Lignin Residue Ash (HLRA) in Com Healt Doumab t Kansas State University cement researcher, Feraidon Ataie, was a winner at the 2013 Capitol Graduate Research Summit in Topeka, Kans., in February. CENTORR Vacuum Industries VI Batch Hot Press Continuous All types of High Temperature Ceramics Processing Vacuum Furnaces PRODUCTION AND LABORATORY All non-oxides: SIC, AIN, BN, TiB2, B4C & Si3N4 Hot Presses from 0.5 to 1500 tons CVI has built over 6,500 furnaces since 1954 • Max Possible Temperature: 3,500°C (6,332°F) • Hot Zones: 10 cc to 28 cu meters (0.6 cu in to 990 cu ft) • • Debind, Sinter, Anneal, Hot Press, Diffusion Bond, CVD, CVI, MIM • CVI testing in our lab to 2,800°C (5,072°F) Worldwide Field Service, rebuilds and parts for all makes Centorr Vacuum Industries, Inc. 55 Northeastern Blvd., Nashua NH 03062 USA Toll free: 800-962-8631 Ph: 603-595-7233 Fax: 603-595-9220 E-mail: sales@centorr.com Details at www.centorr.com/cb American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 21 (Credit: KSU.) ceramics in the environment MIT Concrete Hub updates work on sustainability research Nature offers a new, free-access story by Ivan Amato that updates some of the efforts to lower CO2 emissions and the energy requirements for cement production going on at the Concrete Sustainability Hub (CSHub) at the Massachusetts Institute of Technology in Cambridge. The article particularly focuses on their work to make progress in modeling the calcium silicate hydrate (C-S-H) reactions, and understanding the difference characteristics of its alite and belite phases. Altough the story, \"Green Cement: Concrete Solution\" covers some fairly familiar (if not somewhat misleading) ground, it does suggest that CSHub researchers are getting a better handle on the pros and cons of increasing the belite content of clinker. (Clinker is eventually ground into the powder that is known as portland cement.) The alite phase, abbreviated in cement nomenclature as C3S, is more reactive with water and, therefore, hydrates (cures) in concrete mixtures faster than belite. The downside to alite is that it requires more energy and produces more CO2 emissions than belite (alite forms at about 1,500°C and belite at around 1,200°C.) Thus, the thinking goes that if there was a clever way to make better use of belite, there would be good for the environment. Researchers at the CSHub report in a recent newsletter that they have been investigating the various polymorphs of belite, specifically its B, Y, and three a phases. In particular, they have been using \"first-principles fully quantum mechanical analytical techniques\" to model the various polymorphs. They have combined the modeling with statistical analyses to focus on and predict the most reactive and favorable structures of ẞ and y. They claim to have a deeper understanding of how adatoms (atoms adsorbed into the crystal structure) and defects play a role in determining surface energies and crystal reactivity. 22 Amato notes there is another downside to belite, besides lower reactivity: It is harder and, therefore, requires more mechanical energy to grind, a reality that decreases any potential net energy savings. Billion tonnes cement Projection developing countries India Crieve OECD 1900 2000 2010 2020 2030 Other inadustrial nations 2040 2060 Cement demand is forecast to rise to meet the demands of a growing world population. Some experts, such as Karen Scrivener who leads a Europeanbased research initiative (See interview with Scrivener in June/July 2012 ACerS Bulletin), have doubts that there will be a large payoff to tinkering with the clinker composition. Instead, Scrivener and others think larger gains can be made by replacing a significant amount of the clinker (\"reducing the clinker factor”) by using supplementary cementitious materials (SCMs) that, conveniently, are often byproducts of other industries. These SCMs can include fine limestone, flash, blast furnace slag, silica flume, and natural pozzolans. In fact, the US may lag Europe and other regions in the use of SCMs, which Scrivener says European cement producers over the past two decades have successfully found as substitutes for about 25 percent of the clinker. One major difference, however, between Europe and the US is that the concrete industry, in the former, tends to use mixes containing SCMs that are premade at cement-making facilities, whereas US concrete makers who do use SCMs tend to add the SCMs while mixing the concrete. Waiting until the concrete-mixing stage introduces a significant change for variations from batch to batch. Amato does report on efforts by at least one US company, Ceratech, to produce and market cement mixes that contain flash. But Amato notes, \"Ceratech is a bit player in the cement industry, and its approach to cutting carbon emissions amounts to a mere clink in a multibillion-tonne batch. The big carbon reductions will come only when next-generation cements are embraced by the construction industry\'s thousands of independent producers, engineers, architects, city planners, and building inspectors.\" However, there are some misleading points to Amato\'s article, starting with the title (which, in fairness he may not have written). The admittedly nonintuitive truth is that concrete is already a relatively \"green\" construction material that is far less energy intensive than masonry, steel, aluminum, and even wood. Another inconvenient truth is that cement and concrete construction are absolutely essential to housing and infrastructure development, especially in the developing regions, and that it is unrealistic to imagine an alternative in the remainder of the 21st Century. A final inconvenient truth is that the availability of some of the SCMs is actually very low-including waste slag and fly ash-compared with overall production quantities-and in some cases nonexistent because the regions lack the steelmills and powerplants that generate the byproduct. Therefore, research into the use of more common SCM sources, such as calcined clays and natural pozzolans is expected to yield the most significant sustainability breakthroughs in the future. Scrivener says that a 10-percent reduction in the amount of CO, currently associated with the production of a cubic meter of concrete would be equivalent to removing all of the CO₂ emissions associated with steel production. All of this is not to say that CSHub\'s work is not significant. In fact, it appears that they are doing a lot of valuable computation modeling work that will contribute to worldwide efforts to understand hydration and to build databases that can be used to create custom cement and concrete mixes based on regionally available sustainable resources. Even 1 or 2 percent efficiency gains in clinker production are of value given the enormous amount of www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 (Credit: Karen Scrivener.) cement and concrete produced world wide. Aerogel-based insulation continuing to make progress with commercialization One of the promises of basic silicabased aerogel is that it would make a fantastic component in insulation systems-but there always have been a lot of manufacturing and processing “ifs\" involved. Nevertheless, several companies are starting to make headway with emerging commercial products. In terms of energy consumption, the importance of improved building insulation varies among regions of the globe. Although it is a second-tier concern in North America, the energy-consumption pattern in many European nations is dominated by heating. Germany is one of the best examples, where well over 25 percent of the nation\'s energy consump tion goes into residential and commercial space heating. Much of the problem is related to the age of the building stock. Besides the heat leakage problems that come from very old buildings, remediation is a challenge because of sheer space limitations. Thus, although the availability of aerogel-containing insulation panels and systems may not be front-page news in the United States, it is a fairly big deal in Europe (where the EU already is funding a major research and commercialization initiative). An internal insulation and finishing system developed by STO AG-\"STO in Aevero\"-recently received the \"Award for Product Inno-vation\" at the BAU 2013 trade fair. At least in terms of product recognition, this is a nice accomplishment because BAU probably is the world\'s largest expo for architecture, materials, and systems. STO\'s system uses aerogel develop by Cabot. Sixty companies were part of the competition, vying for three prizes and six awards. The STO/Cabot system won the event\'s \"Investing in the Future\" award. A Cabot news release describes the product as a \"super slim system comprised of a composite board that combines Cabot\'s aerogel particles for superior energy-savings performance with STO\'s binder and composite technology. This results in an insulation board that offers greater energy efficiency than traditional Bioactive Glass Engineering for a better life materials. Cabot\'s aerogel enables an ultralow thermal conductivity of 0.016 W/mK applied in very thin insulation thicknesses from 10 to 40 millimeters (R3.5 - R14).\" mo.sci CORPORATION Bioactive and biocompatible compositions in the silicate, borate, and phosphate glass families are available. Custom compositions are welcomed. Mo-Sci specializes in final form manufacturing which includes frit, fibers, ribbon, spheres, cast objects, and porous materials. The innovative staff at Mo-Sci will work with you to design and develop your project. Mo-Sci is ISO 9001:2008 and AS9100C certified. mo.sci HEALTH American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org CARE mo.sci SPECIALTY PRODUCTS www.mo-sci.com 573.364.2338 mo-sci PRECISION MATERIALS 23 24 Commercial Yb:SiO2 fiber Yb: YAG-derived all-glass fiber (Credit: P. Dragic; UIUC.) Cooperative up-conversion from an infrared laser excited sample of Yb-doped conventional optical fiber (left) versus that from an all-glass fiber whose core is made from YAG crystal under equivalent excitation conditions. Such visible up-conversion of light is deleterious to the desired infrared performance and so less is better. O bulletin | cover story Molten-core fabrication of novel optical fibers By Stephanie Morris and John Ballato The molten-core approach allows simple fabrication of novel optical fibers-for use in high-energy lasers, telecommunication devices, and sensors-in long lengths from not-so-novel crystalline and amorphous materials. W Whether seeking to explain physical phenomena, as did such luminaries as Huygens in 1690,¹ Newton in 1704,2 and Maxwell in 1873,³ or routes to truth and enlightenment, as did Shakespeare in 1598 (\"Light, seeking light, doth light of light beguile\"), light fascinates us. 4 Beyond the physical, metaphysical, and poetic, light is immensely useful and central to modern life as detailed in the recent report \"Optics and photonics, essential technologies for our nation,\" published by the National Research Council of the National Academies.5 For example, the report notes that photonics enables more than $7 trillion in global products, equivalent to about one-half of the Gross Domestic Product (GDP) of the United States. The European Physical Society, representing the 41 national physical societies in Europe, is coordinating a proposal for the proclamation by the United Nations for an International Year of Light in 2015. This proposal received enthusiastic support from UNESCO. The technological utility of light is remarkably broad. Therefore, for the purposes of this report, let us focus on one subset: optical fiber. Beyond the awarding of the 2009 Nobel Prize in Physics to Charles Kao “for groundbreaking achievements concerning the transmission of light in fibers for optical communication,\" present and future demands for information have caused a dramatic shift from long haul and regional deployments to broadband. As a result, optical fiber production is projected to increase from about 150 × 10+ km/year of fiber at present to much more than 200 × 106 km/year by 2017.6 Although the vast majority of this fiber will be for \"conventional\" telecommunication applications, there are growing needs for specialized optical fibers, i.e., those providing greater or enhanced functionality. Specific applications drive demand for higher-performance optical fibers, for example: • Deep-well gas and oil sensors deployed at extreme temperawww.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 (Credit: Ballato; Clemson University) tures, pressures, and chemical environments; High-energy laser systems, where optical nonlinearities, such as stimulated Brillouin scattering (SBS), limit continued power-scaling; and • Highly nonlinear glasses for alloptical signal processing (not just amplification), in optical communication systems.⁹ 9 Two general trends contribute to enhanced performance from fibers. Historically, new materials with properties not available in conventional optical glasses (like silica) are developed. Examples include fluoride glasses for reduced losses and more efficient light emissions from active dopants, or tellurite and chalcogenide glasses for extended infrared transparency and stronger optical nonlinearities (e.g., strong nonlinear refractive index, n). The more recent trend accepts the material limitations of silica and focuses instead on inducing optical behaviors through the microstructure. Examples of microstructure engineering include microstructured optical fibers (MOFs) or photonic crystal fibers (PCFs). Periodicity in the refractive index, which comes from periodic combinations of silica rods and tubes constructed and drawn into fiber, controls various aspects of the electromagnetic mode propagating down the fiber. Such MOFS and PCFs can exhibit marked changes to the fiber\'s dispersion, nonlinearity, and spectral loss even though the composition is still silica. This report proposes a third option: novel fibers from not-so-novel materials and a return to simplicity. Specifically, the article summarizes recent developments using materials that are new with respect to optical fibers but familiar to the broader materials community, such as silicon and sapphire. They are commodity materials in their own right but novel and nonobvious materials with respect to glass optical fibers. These materials offer a variety of extraordinary properties and provide a rich playground for continued materials science, includ ing novel all-glass, 10,11 glass-clad crystalline core, 12 and crystalline optical fibers. New approach for drawing fiber Several methods exist to fabricate optical fiber from nontraditional and dissimilar core and clad materials, and each has distinct advantages and disadvantages. Early techniques include the Taylor wire method,¹³ which implements fast quenching rates to create glass-coated metal wires in a relatively inexpensive manner. The Wollaston wire approach also has been used to draw fibers from differing core and cladding materials, particularly those exhibiting steep viscosity-temperature behaviors. 14 The Wollaston method is useful for drawing fibers from materials that tend to devitrify, such as fluorozirconate glasses. However, materials must be chosen with care to ensure the chemically aggressive fluorozirconate melt does not attack the cladding glass. A \"core-suction\" technique fabricates multicomponent glass-core preforms by melting and drawing-up the core glass melt into a cladding tube under vacuum.15 The core material must necessarily melt at a lower temperature than the cladding tube material. With respect to crystalline fibers, laser-heated pedestal growth (LHPG) and micro-pull-down techniques have been well studied and used with increasing .16 However, these methods are slow in the grand scheme of fiber fabrication methods (e.g., draw), and achieving a high-quality core-clad interface can be difficult. success. Success using these approaches to make fibers from glasses (fluorides, tellurites, chalcogenides) and crystals (metallic and oxide) varies. Another class of materials-semiconductors-has profoundly impacted electronic and optoelectronic applications. Indeed, silicon photonics is a rapidly growing area of global interest, 17 and extending semiconductors to opticalfiber formats would open up entirely new opportunities. The field of semiconductor optical fiber, though nascent, relies on two principal fabrication methods. The first method is a high-pressure microfluidic chemical vapor deposition (CVD) of the semiconductor inside a silGlass cladding Molten core Figure 1. Schematic representation of the molten-core approach. ica microstructured optical fiber. 18 This method is a sufficiently low-temperature process that either amorphous or crystalline semiconductors can be deposited as can layers of different semiconductors to fabricate in-fiber optoelectronic junctions. Further, the deposition can be done in silica MOFS with small core sizes. However (relative to a molten-core method described next), CVD is limited by slow deposition rates and relatively short fiber lengths. To date, silica-clad fibers with cores of amorphous or crystalline silicon and germanium have been made as have zinc selenide-based fibers.19 Semiconductor optical fibers also have been made using a powder-intube method 20 and a melt-infiltration approach.21 The second method, an alternative approach and the focus of this article-is the molten-core method, which allows the direct fiberization of a range of unconventional core materials, either amorphous or crystalline. It is versatile, practical, and yields long lengths of optical fiber. In general, a precursor core phase is set inside a tube, which serves as the cladding glass (Figure 1). At the temperature where the cladding glass tube draws into fiber, the core precursor phase is molten. As the cladding glass draws into fiber, the fluent core melt goes \"along American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 25 Molten core fabrication of novel optical fibers BGC relative to conventional silica (dB) 0 10 20 30 40 50 60 70 80 90 0 -10 -20 20 -30 -40 -50 -60 60 70 -80 -90 0 10 20 50 60 \"ZeBrA\" condition 30 40 70 Average alumina concentration (mol%) 80 90 100 100 Figure 2. Calculated Brillouin gain coefficient for sapphire-derived fibers (recast from Ref. 24). The green dots represent fiber core compositions that have been fabricated to date. for the ride\" and ultimately solidifies as the fiber cools. Originally developed as a means to make all-glass fiber with core compositions not stable enough to form into rods and draw directly,\" the molten-core method enables making long lengths of fiber directly from a simple preform and from a range of common materials such as silicon, germanium, YAG (Y,ALO), and alumina. 22-24 Although the process is straightforward, the materials science of what happens during the process is not. The melt (core) contacts the softened glass (clad) at the interface, and the two necessarily interact via dissolution and subsequent diffusion. Because dissolution is a thermally activated process, higher draw temperatures lead to more dissolution. The composition shifts from the precursor phase to the final core phase. In actuality, the cladding actively dopes the core during fiber drawing. This is fundamentally different, and in many ways opposite, from the conventional approach to making fiber compositions where the silica host is doped with the modifying additives either in the vapor phase or in the solution phase. With the molten-core approach, the mol26 ten core dissolves some of the glass cladding and brings its constituents into the resulting core phase. Thus, a wider range of core compositions is possible. This dissolution and compositional “drift” is a blessing and a curse depending on what is desired in and of the fiber. Novel all-glass crystal-derived optical fibers Technically, as long as the initial core phase is molten at the draw temperature, there is no reason any particular phase cannot be used. However, practical considerations limit selection, such as restricting materials with high vapor pressures, which can (and do) blow out the softened glass cladding tube during the draw. That said, whether the initial core phase is a glass, single crystal, polycrystal (ceramic), or powder is immaterial as long as it melts at the draw temperature. In the case of powders, bubbles in the melt resulting from the porosity of the powder can be a concern. An advantage of starting with crystalline core phases is the ability to use phases that cannot otherwise be made into glass. Two exemplars of this are YAG-derived 23-25 and sapphire-derived²4 optical fibers fabricated using the molten-core approach. Yttria and alumina additions to silica reduce the glasses\' Brillouin gain, which thereby lessens the potential for stimulated Brillouin scattering (SBS) in optical fibers. SBS is a principal limitation in high-power fiber lasers and high-capacity telecommunication systems. Liquid-liquid immiscibility in the Y2O3-SiO2 and Al2O3-SiO2 melt restricts the range of compositions to those with high silica content. However, in both cases, silica dissolves into the core from the (pure silica) cladding glass at the approximately 2000°C draw temperature and promotes the formation of yttrium aluminosilicate (for YAGderived) or aluminosilicate (for sapphirederived) glass cores because of the high quench rates of the drawn optical fibers. The resultant core glasses contain much higher yttria and alumina concentrations than would otherwise be possible, opening the door to \"novel fibers from common materials” (just not common when it comes to optical fibers). For example, the YAG-derived fibers with high yttria and alumina contents have shown less cooperative up-conversion and photodarkening than conventional silica-based fibers (demonstrated in images at top of article on previous page). As another example, the sapphire-derived fibers have alumina concentrations up to about 54 mol%, which is the highest alumina concentration reported for a silicate glass not made using more extreme methods, such as melt levitation. By comparison, given the immiscibility and time-temperature requirement on conventional CVD optical fiber preforms, the typical limit to alumina content is about 8 mol%. Also, the melt viscosity increases and liquidus temperature decreases as the alumina melt dissolves the silica cladding glass, further hindering the phase-separation of the high-alumina-content core glass. The lowest reported Brillouin gain coefficient nearly 100 times lower than conventional silica fibers-was in sapphire-derived high-alumina-content aluminosilicate glass optical fibers (Figure 2). Further, an aluminosilicate composi tion was shown to be Brillouin athermal www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 (a) (b) (c) 500um 50 Dum Figure 3. Electron micrographs of (a) silicon, (b) germanium, and (c) InSb crystalline core optical fibers. (After Ref. 22) (i.e., the Brillouin frequency does not change with temperature), which could have applications in novel sensor and laser systems with Brillouin performance immune to temperature fluctuations. There also are compositions that conceivably could exhibit zero Brillouin scattering, so-called zero Brillouin activity (ZeBrA) fibers. The structural origins of zero Brillouin, hence no photoelasticity, glasses are under study and could be exceedingly useful to future fiber-based laser and communication systems. Novel glass-clad crystalline-core optical fibers As noted previously, it is reasonable to expect that molten-core-derived fibers will have amorphous cores, given the quench rates of the drawn fibers. However, although it is nonobvious, the process also yields long lengths of glassclad fibers with polycrystalline cores. For example, Figure 3 shows cross sections of fibers drawn from technologically important unary and binary semiconduc tors, including silicon, germanium, and InSb. As before, a tube of glass clads a rod of the crystalline phase. The glass composition is chosen such that it draws above the core material\'s melting point. Successful glass-clad-core compositions include silica cladding for silicon, borosilicate glass cladding for germanium, and phosphate glass cladding for InSb. Because silicon, germanium, and InSb have cubic crystal structures and are, therefore, optically isotropic, polycrystallinity itself is not problematic. In terms of the polycrystallinity, X-ray diffractometry (XRD) studies show that single-crystal grains are up to 15 mm long. This is quite remarkable for a fiber drawn at a speed of about 1 m/s. That said, impurities tend to aggregate at grain boundaries, which can lead to scattering and increased losses. Additionally, even in the lowest-temperature case (InSb drawn at about 700°C), the melt dissolves some of the cladding glass and brings those species into the core. In the aforementioned case of the YAGderived and sapphire-derived fibers, the cladding species facilitates glass formation, for example, silica dissolves into the Y2O3 + Al2O3 melt. In the case of semiconductor cores, these (oxide) cladding glass species in the melt precipitate out as amorphous nanophases, but still permit the formation of polycrystalline semiconductor phases. The precipitated oxides scatter light as it propagates down the fiber. This is a key issue that needs resolution for the technology to advance. Nonetheless, the molten-core-derived silicon and germanium fibers remain the lowest-loss semiconductor fibers fabricated to date. These crystalline-core fibers present an intriguing fundamental question concerning the interplay between thermodynamics and kinetics in this system. An advantage of the molten-core approach is the ability to create long lengths of fiber at commercially relevant speeds. If one assumes that the rate of crystallization of an amorphous material is roughly equivalent to the critical velocity for amorphization, then the upper limit of draw speeds has yet to be approached.²² These unary semiconductors behave as anomalous liquids, i.e., the solid floats on top of the liquid (melt). This phenomenon combined with the molten-core approach prevents undissolved material from passing through the neckdown region and into the drawn fiber, thus assuring greater core homogeneity. American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 00m Further investigations will define the roles of fiber structure-property relationships, such as the influence of core geometry on the crystallography of the semiconductor-core phase and the influence of tapering. For example, fibers fabricated with square cores have higher degrees of single crystallinity, and the <110> crystallographic direction is dominantly aligned with the longitudinal axis of the fiber, a significant departure from the 35 percent exhibited in the roundcore fibers.26 Reactive molten-core fabrication A particularly fascinating and important feature of the molten-core approach to optical fiber fabrication is that chemical reactions can occur in-situ during the fiber drawing as part of the process. That is, species can volatize away from reactive metals, or chemical reactions can take place. Either mechanism leads to final core compositions very different from those of the precursor phases. With respect to chemical reactions during fiber formation, the molten-core approach was used to fabricate oxygenfree, silica-clad crystalline silicon cores despite being processed at 2000°C. 27 In this example, SiC powder mixed with the precursor silicon acts as a getter for the oxide that enters the core melt from the silica cladding tube dissolution. The reaction byproducts at the draw temperature are solid silicon and SiO(g) and CO(g), both of which evolve out of the fluent melt. A crystalline silicon-core optical fiber clad in silica with negligible oxygen results, as shown in Figure 4. Although there still are optical losses, probably because of other impurities or defects in the silicon, scattering reduces measurably, an important step. 27 Molten core fabrication of novel optical fibers (a) Si (Ka) (b) (c) Figure 4. (a) Scanning electron micrograph of a silica-glass-clad silicon-core optical fiber drawn using a reactive molten core of Si + SiC. Energy dispersive spectroscopic spatial maps qualitatively show the concentration of (b) silicon and (c) oxygen, where the brighter region indicates higher elemental content. (After Ref. 27) Volatility, as a form of reactive chemistry, was originally used in 1989 to produce novel silica-glass fibers for optical amplification.10 Recently, molten-core drawing achieved glass-clad crystalline oxide core optical fiber in the Bi₂O₂GeO2 system. In this case, a borosilicate glass cladding tube filled with precursor crystalline powders of stoichiometric Bi₁2GeO20 yielded either amorphous or crystalline optical fibers, depending on the draw conditions. 28 The all-glass fibers had core compositions with about 70 mol% Bi₂O3, which is significantly higher than previously reported values for bismuth-containing fibers. Powder XRD showed the crystalline core fibers were biphasic, containing Bi̟O̟ and Bi̟GeO. Although the polycrystallinity and multiphase nature led to high levels of light scattering, these results were significant. For the first time, an industrially scalable manufacturing process was employed to make optical fibers with crystalline oxide phases. Also, B₁₂GeO, is acentric which, with further development, could lead to long lengths of glassclad optical fibers with useful optoelectronic properties, including piezo-optics, second-harmonic generation, and related optical nonlinearities. More opportunities ahead The molten-core approach is a flexible method for producing optical fibers from unconventional materials-crystalline and amorphous-over long lengths using scalable processes. From in-situ reactive melt chemistries to the realization of concentrations of alumina otherwise unattainable, this method allows 28 fabrication of novel optical fibers for applications ranging from high energy lasers to telecommunications and sensing. Equally important, there are rich opportunities for materials science experiments using this method, including fundamental studies of thermodynamics, kinetics, crystallization, and phase diagrams. Acknowledgments The authors wish to thank the following individuals for thoughtful and timely input: Bob Rice (Dreamcatchers Consulting), Pete Dragic (University of Illinois), Anna Peacock (Southampton University), Thomas Hawkins (Clemson University), Paul Foy (Clemson University), and Roger Stolen (Clemson University). A Brillouin glossary About the authors John Ballato is director and founding member of South Carolina\'s Center for Optical Materials Science and Engineering Technologies (COMSET) and professor in the Department of Materials Science and Engineering, Clemson University, Clemson, S.C. Stephanie Morris is a graduate student in Clemson\'s Department of Materials Science and Engineering and will join Corning Incorporated after graduating in May. Correspondence should be directed to John Ballato at jballat@clemson.edu. References ¹C. Huygens, Traité de la Lumière (Leyden, 1690); English translation by S.P. Thompson, Treatise on Light, Macmillan, London, 1912. 21. Newton, Opticks (London, 1704); Reprinted by Dover Publications, New York, 1979. Leon Brillouin (1889-1969) earned his PhD from the University of Paris in 1920, where he later became a professor of theoretical physics (1928-1932). He emigrated to the United States in 1941 and conducted research in applied mathematics and solid-state physics at Columbia University (1943-1945) and Harvard University (1947-1949) prior to joining IBM. Brillouin scattering is a form of anelastic scattering between a light wave and phonons from the material through which the light is propagating. Brillouin frequency is the anelastic nature of the scattering that results in a shift in the frequency (energy) of the light wave, which is analogous to the classical Doppler shift. This frequency shift is equal to the energy of the interacting phonon and, hence, is characteristic of the material and depends on the wavelength of the incident light. Brillouin gain (coefficient) occurs if the light wave is sufficiently intense. Then, the Brillouin scattering can become stimulated whereby the forward propagating beam interacts strongly with an electrostrictively induced back-scattered wave. The strength of this gain is given by a gain coefficient. Although Brillouin first predicted the phenomena in 1922, Russian physicist, Leonid Mandelstam (1879-1944) is believed to have theorized the same scattering in 1918. However, Mandelstam did not publish his work until 1926. To give complete credit, the effects also are referred to as \"Brillouin-Mandelstam scattering.\" www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 J.C. Maxwell, A treatise on electricity and magnetism, Oxford University, Oxford, U.K., 1873. 4W. Shakespeare, Love\'s Labor\'s Lost, Act 1, Scene 1, Verses 72-79. 5Optics and Photonics, Essential Technologies for Our Nation, ISBN: 978-0-309-26374-0SBN-13, 2012. \"C.D. Chafee, \"The market for fiber optic components: A seven year forecast (2011-2017),\" Laurin Publishing, Pittsfield, Mass. (A summary is available at http://www. photonics.com/Article.aspx?AID=49953). \'S. Aref, M. Zibaii, and H. Latifi, \"An improved fiber optic pressure and temperature sensor for downhole application,\" Meas. Sci. Technol., 20, 034009 (2009). 8J. Dawson, M. Messerly, R. Beach, M. Shverdin, E. Stappaerts, A. Sridharan, P. Pax, J. Heebner, C. Siders, and C. Barty, \"Analysis of the scalability of diffractionlimited fiber lasers and amplifiers to high average power,\" Opt. Express, 16, 13240-66 (2008). ⁹T. Monro, H. Ebendorff-Heidepriem, W. Zhang, and S. Vahid, \"Emerging nonlinear optical fibers: revised fundamentals, fabrication, and access to extreme nonlinearity,\" IEEE J. Quant. Electron., 45, 1357-64 (2009). 1ºE. Snitzer and R. Tumminelli, “SiO₂-clad fibers with selectively volatilized soft-glass cores,\" Opt. Lett., 14, 757-59 (1989). J. Ballato and E. Snitzer, \"Fabrication of fiber with high rare-earth concentrations for Faraday isolator applications,” Appl. Opt., 34, 6848-54 (1995). 12J. Ballato, T. Hawkins, P. Foy, R. Stolen, B. Kokuoz, M. Ellison, C. McMillen, J. Reppert, A. M. Rao, M. Daw, S. Sharma, R. Shori, O. Stafsudd, R.R. Rice, and D.R. Powers, \"Silicon optical fiber,” Opt. Express, 16, 18675-83 (2008). 13G. Taylor, \"A method of drawing metallic filaments and a discussion of their properties and uses,” Phys. Rev., 23, 655-60 (1924). 14D. Furniss, J. Shephard, and A. Seddon, “A novel approach for drawing optical fibers from disparate core/ clad glasses,\" J. Non-Cryst. Solids, 213, 141-46 (1997). 15N. Goel, R. Stolen, S. Morgan, J. Kim, D. Kominsky, and G. Pickrell, “Core-suction technique for the fabrication of optical fiber preforms,” Opt. Lett., 31, 438-40 (2006). 16W. Wang, J. Wang, Y. Huang, Li. Liu, S. Huang, and W. Cheng, \"Few-mode Cr-doped crystalline core fibers for fiber amplifier,\" IEEE Photon. Technol. Lett., 24, 1628-31 (2012). 17R. Soref, \"Silicon photonics: A review of recent literature,\" Silicon, 2, 1-6 (2010). 18N. Baril, R. He, T. Day, J. Sparks, B. Keshavarzi, M. Krishnamurthi, A. Borhan, V. Gopalan, A. Peacock, N. Healy, P. Sazio, and J. Badding, “Confined high-pressure chemical deposition of hydrogenated amorphous silicon,\" J. Am. Chem. Soc., 134, 19-22 (2012). ¹ºJ. Sparks, R. He, N. Healy, M. Krishnamurthi, A. Peacock, P. Sazio, V. Gopalan, and J. Badding, \"Zinc selenide optical fibers,\" Adv. Mater., 23, 1647-51 (2011). 20B. Scott, K. Wang, V. Caluori, and G. Pickrell, \"Fabrication of silicon optical fiber,” Opt. Eng., 48, 100501 (2009). 21H. Tyagi, M. Schmidt, L. Sempere, and P. Russell, \"Optical properties of photonic crystal fiber with integral micron-sized Ge wire,” Opt. Express, 16, 17227-36 (2008). 22J. Ballato, T. Hawkins, P. Foy, B. Yazgan-Kokuoz, C. McMillen, L. Burka, S. Morris, R. Stolen, and R. Rice, \"Advancements in semiconductor core optical fiber,” Opt. Fiber Technol., 16, 399-408 (2010). 2³J. Ballato, T. Hawkins, P. Foy, B. Kokuoz, R. Stolen, C. McMillen, M. Daw, Z. Su, T. Tritt, M. Dubinskii, J. Zhang, T. Sanamyan, and M. J. Matthewson, \"On the fabrication of all-glass optical fibers from crystals,\" J. Appl. Phys., 105, 053110 (2009). 24P. Dragic, T. Hawkins, S. Morris, and J. Ballato, \"Sapphire-derived all-glass optical fibers,” Nature Photon., 6, 629-35 (2012). 25P. Dragic, P.-C. Law, J. Ballato, T. Hawkins, and P. Foy, \"Brillouin spectroscopy of YAG-derived optical fibers,\" Opt. Express, 18, 10055-67 (2010). 26S. Morris, C. McMillen, T. Hawkins, P. Foy, R. Stolen, R. Rice, and J. Ballato, \"The influence of core geometry on the crystallography of silicon optical fiber,\" J. Crystal Growth, 352, 53-58 (2012). 27S. Morris, T. Hawkins, P. Foy, C. McMillen, J. Fan, L. Zhu, R. Stolen, R. Rice, and J. Ballato, \"Reactive molten core fabrication of silicon optical fiber,” Opt. Mater. Express, 1, 1141-49 (2011). 28J. Ballato, C. McMillen, T. Hawkins, P. Foy, R. Stolen, R. Rice, L. Zhu, and O. Stafsudd, \"Reactive molten core fabrication of glass-clad amorphous and crystalline oxide optical fibers,” Opt. Mater. Express, 2, 153-60 (2012). Increase Your Knowledge with a 2013 ACerS Ceramic Materials Short Courses Sintering of Ceramics June 1-2; Oct. 31-Nov. 1 | M. Rahaman Fundamentals of Glass Science June 5-6; Oct. 26-27 | A.Varshneya Dispersion and Packing of Ceramics Particles for Advanced Refractory Castables Sept. 10 | V.Pandolfelli; A. Luz; M. Braulio Fundamentals on Corrosion Behavior of Refractories Sept. 10 | C. Aneziris; J. Poirier Electroceramics Basics: Applications and Devices Oct. 31 | R. Pandey The American Ceramic Society www.ceramics.org www.ceramics.org/shortcourses American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 29 30 30 Wound Dimensions (mm) Initial Day 159 160 •Length Width Depth 140 120 100 1.6mm/day 80 60 40 1.0mm/day 20 0 50 100 150 vanced Patent DB m Patient Profile 39 yr old M paraplegic (motorcycle accident) Age of wound unknown Etiology: Sacral ulcer over bony prominence (lower back, tail bone) Drainage noted \'Killer Wound\' Days of Treatment Although most of the patients treated with DermaFuse had wounds related to diabetes, one paraplegic patient had an extreme bedsore successfully healed. Wound healing: An update on Mo-Sci\'s I It was two years ago when I did my first interviews and wrote the original public story about novel glass fibers, a piece that startled many in the medical community. My ACerS Bulletin (\'Cotton candy\' that heals?; May 2011) was about a company, Mo-Sci Corp., that had leveraged research conducted at the Missouri University of Science and Technology. (MS&T) and developed a unique and pernovel borate haps revolutionary medical product. Dubbed glass fibers By Peter Wray DermaFuse, this product is composed of a special formula of cottony borate glass nanofibers that appear to have a knack for healing deep, complicated, and long-standing wounds. At the time, the \"news\" in the story was, first, that human studies-not just animal trials-had been underway among a small group of mainly diabetic patients at the Phelps County Regional Medical Center (PCRMC) in Rolla, Mo. The second news nugget was that seven of the 11 patients being treated with the borate fibers already had their wounds healed, with little scarring, at a speed equal to or faster than expensive state-of-the-art healing www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 (Credit: Mo-Sci.) products and had been released from care. Moreover, the other four patients were well on their way to healing. Everyone involved admitted that the results were preliminary and based on a relatively tiny group. But, they also noted that the medical professionals involved had been \"going by the book\" and documenting each case. A PCRMC nurse who specializes in nonhealing wounds, Peggy Taylor, delivered the care to each patient under the supervision of a hospital physician. Moreover, the institution\'s Internal Review Board monitored the entire trial. But, the universal question at the time the story was published was, were the benefits of DermaFuse a fluke or would the results hold up in an expanded trial? Two years and more than 50 new patients later, the answer is that effects of DermaFuse treatment have been identically beneficial and that the aggregated results are just as stunning and paradigm shifting as they were in 2011. A little review To recap, DermaFuse was developed by two MS&T glass researchers, Delbert Day and Steve Jung. Day, a renowned MS&T professor and glass innovator, already had established Mo-Sci to commercialize several of his previous discoveries. Jung joined Mo-Sci as a senior researcher, a role that would allow him to continue developing applications for their fluffy new glass-fiber material. Day and Jung told me they had a hunch about the glass because of its calcium content and its dissolution behavior. They said that other researchers reported the presence of calcium as an important factor in the wound healing of skin, especially in late stages, and suggested that it is required for the migration of epidermal cells. Other researchers found that the presence of calcium in the immediate vicinity of an open wound helps the body to regulate the wound-healing processes more effectively. This latter point about helping the body\'s own wound healing process is likely a key factor. In fact, the suggestion in the title of my original article was somewhat misleading. The cottonInitial Discovery In-vivo Animal Testing Filed Intellectual Property ISO-10993 Biocompatibility Testing Exploratory Human Trials Packaging/Labeling/Sterilization Validation Manufacturing Validation FDA Device Master File Engage USFDA about Pivotal Human Trial FDA 510K Submission Completed In Progress Future Work Commercialization Chart showing progress of DermaFuse toward FDA approval and commercialization. candy-like glass fibers, themselves, do not do the healing. The fibers do provide an immediate clotlike structure and create an antimicrobial environment. These important benefits create a positive environment, but they are only the beginning. Day, Jung, and many others in the biomedical glass materials field theorize that the larger and most important effect comes from the material sending a signal to the body to do the healing of which it is capable. In other words, as components of the glass dissolve and various ions are absorbed at the wound site, the chemical effect somehow taps into and stimulates innate cellular and genetic healing processes. In this sense, DermaFuse represents what some are calling the \"Third Generation\" of biomedical materials, a group of glass, ceramics, and other materials designed to generate specific cell responses to the controlled release of biochemical stimuli (See, \"Three generations of biomedical glass and other bioceramics,\" p. 32). The form factor of DermaFuse is very simple and makes the material easy to use. Mo-Sci typically manufactures and packages DermaFuse in bandage-sized pads. In 2011, Peggy Taylor, RN, told me that she treated wounds by either using the material as supplied or easily fluffing it up to a cotton ball shape. The cotton ball form was particularly useful because of the type of wounds Taylor was treating in the initial group of patients. All except one of the patients American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org (Credit: ACerS.) (Credit: Mo-Sci.) Peggy Taylor, a certified wound and ostomy care registered nurse, holds a packet of Mo-Sci\'s DermaFuse. Taylor has been conducting the treatment of patients in PCRMC\'s clinical wound healing trials. were diabetics with \"venous stasis\" wounds on their lower extremities. These types of wounds are prone to infection and frequently lead to amputation unless they are treated with expensive and often difficult to use approaches and equipment, such as vacuum-based therapy (e.g., \"wound VAC\"). Venous stasis wounds and pressure ulcers (bedsores) are a concern because, although they start small, they can quickly expand and grow deep, painful cavities below the skin surface. Taylor found that she could easily pack even the deepest wounds with DermaFuse and simply apply a protective covering. 31 Wound healing: An update on Mo-Sci\'s novel borate glass fibers Peggy Taylor talks with Mo-Sci president Ted Day at the PCRMC wound clinic. Disinfecting or debriding the wound of damaged tissue was not particularly necessary. Taylor said that, as predicted, DermaFuse seemed to block infections, and the first application of the dressing seemed to cause the wound to naturally slough off dead and dying cells. Remarkably, within a few days, the DermaFuse fibers would disappear, (Credit: ACerS.) apparently dissolved and absorbed into the body. In some cases, a small residue composed of tiny glass grains and dead tissue remained, which she would flush and then apply the next application of the DermaFuse. Until she became the lead nurse in the first DermaFuse trials, Taylor had been a fan of wound VAC therapies. Despite the high cost (around $1,200 per week) and clumsiness of the patient carrying a vacuum pump, she appreciated the fast, effective results obtained with the wound VAC approach. But, after seeing the healing that occurred among her first 11 DermaFuse patients, she said, \"Don\'t get me wrong. I am a major fan of the wound VAC. But, as a nurse, if I can see that tissue healing at a similar rate, I am really happy to see some magic happen in that wound bed that would otherwise require very expensive treatments.\" More patients, more success I had heard that the medical center\'s IRB, based on the overwhelming initial success, had approved enrolling several dozen more patients in the DermaFuse trials during the past two years Therefore, I recently checked in with Jung and Ted Day, Delbert Day\'s son and current owner of Mo-Sci, about where things stand with the new patients, new glass compositions, and how the route to commercialization looked to them. Jung confirmed that more patients had been enrolled in the study. \"The IRB allowed us to enroll more than 50 new patients in the DermaFuse treatment study. Peggy Taylor continues to oversee the treatments in her well-equipped 1,500-square-foot clinic,\" he says. Day says that a total of 35 patients have been healed to date, and there are several that are in the process of comThree generations of biomedical glass and other bioceramics How close are all of us to some of the world\'s most advanced glass biomaterials? You may have already swished some of them around in your mouth if you live outside the United States and are a fan of Sensodyne products, especially its \"Repair and Protect\" toothpaste. The toothpaste is sold throughout Europe and many other parts of the world. It contains tiny particles of 45S5 Bioglass developed by ACers Distinguished Life Member Larry Hench. Repair and Protect, made and first distributed by Glaxo Smith Kline (GSK) in 2011, is an effective and simple treatment for teeth with painful temperature and foods sensitivities. This sensitivity is very common and typically results from the deterioration of the hard enamel surface that protects the sensitive inner dentin layer. In brief, the 45S5 glass, composed of Na₂O-Ca0-P205-SiO2, starts to work when it begins to break down the presence of saliva, and its ionic components go into action. Several ion-exchange and surface reaction stages are involved. Eventually a calcium phosphate layer forms and crystallizes to form hydroxylapatite (HA), which is similar chemically and structurally to the minerals in teeth. The HA \"repairs\" in the sense that, according to the GSK website, it fills the tiny holes and tubules in dentin that allow sensations like sweet, hot, or cold to reach nerves and cause pain. The HA also \"protects\" by forming a layer over the tooth that, if used regularly, can prevent further deterioration. In addition, Hench says the 45S5 creates an antimicrobial environment that, research suggests, may offer protection to soft tissue around the tooth. Hench uses the Sensodyne toothpaste and is happy with the results, but he is even happier about the toothpaste for larger reasons. \"GSK\'s product is a breakthrough,\" he says. \"What\'s important about Repair and Protect is that it is the first step in getting scientists, health professionals, and the public to accept that a bioceramic material can be used to prevent deterioration. Prevention of this type is something that government, academic, and private sector researchers should focus on more in the future, because it is much less expensive to prevent deterioration than it is to repair or regenerate tissue.\" Hench has been working on the development of glass and other bioceramic materials for health care applications for several decades. He sees Repair and Protect, as well as Mo-Sci\'s DermaFuse glass, as being representative of what he calls the \"third generation\" of biomaterials. In a talk at the ICACC\'13 meeting in January of this year, Hench explained his historical perspective in terms of various generations of biomaterials. He said the \"first-generation\" materials, developed in the 1960s to 1980s, are characterized by biological \"inertness,\" i.e., they prevent rejection by minimizing the biological response to a foreign body. The principle of inertness, he says, still works adequately for patients who have a lifespan of 10-15 years and are less active. However, because of situations involving, for example, orthopedic implants where the application is expected to last much more than 15 years, the research emphasis shifted and a \"second generation\" of bioactive materials evolved. These include porous implants, powders, and coatings on metallic prostheses to provide a superior, bioactive fixation. The emergence of the third generation of biomaterials has been necessary, Hench says, because, \"All man-made biomaterials used for repair or restoration of the body represent a compromise. No man-made material can respond to changing physiological loads or biochemical stimuli, as do living tissues. This 32 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 pleting that trial. He notes that by keeping the total patients in the group under 60, the testing is actually considered a “pre-clinical\" trial. He reports that after the results came out in 2011, PCRMC has had patients referred from around the state. Jung says the larger pool has provided patients with some different types of wounds-and success stories. \"One of the wounds involved a deep foot wound that had existed for about two years. Another patient was a nondiabetic paraplegic who had developed a large and potentially fatal sacral bedsore. With DermaFuse treatments, the foot wound healed in one month and the sacral wound healed in approximately five months.\" Another patient, Jung says, put DermaFuse\'s antimicrobial powers to a significant test. \"A doctor referred one patient who was not responding to treatment for necrotizing fasciitis, better know as flesh-eating bacteria. Taylor put the DermaFuse on the infected wound and it stopped the progress of the fasciitis within days and started the healing process,\" he says. There have been a few disappointments in treatment, too. \"We have had a couple of patients who really didn\'t experience much improvement in their wounds with DermaFuse. Those were wounds from radiation, such as from cancer treatments, but there is nothing to date that works on those wounds,\" Jung recounts. \"It would have been wonderful and a huge surprise if the DermaFuse had worked in those situations.\" Jung says that one hurdle Mo-Sci has faced is perception. “Medical professionals, materials scientists, and the general public tend to associate glass and ceramic biomedical materials with joint and bone applications,” he says. “When I go to technical meetings, I still mainly hear about bone applications. Thinking about glass for use with wounds and soft tissue isn\'t intuitive. Often we have to break through these preconceptions and have people also start thinking about glass as a \'delivery system\' that stimulates the body\'s own healing process.\" Ted Day, agrees, explaining that discussions between Mo-Sci and the medical community during the past two years have helped them get a better feel for the size of the problem of wound healing is and what type of impact DermaFuse might have. \"Wound care is actually about 10 times larger [than bone applications] in terms of a global market. So, we are talking about somewhere in the neighborhood of $20-30 billion a year.\" Although wound healing is a huge problem globally, Day says it is expected to be an especially serious problem in the near future in the United States because of its aging population and the increase in diabetes. \"More than 25 million Americans have diabetes, and more than six million have problems with wounds,\" says Day. \"But, it\'s more than just diabetes. As our population ages and grows, more people will be in nursing homes where, unfortunately, bedsores Sensodyne \"Repair and Protect\" toothpaste awaits FDA approval before it can be sold in the US. SENSODYNE compromise limits the lifetime of all manmade body parts.\" Hench defines third-generation biomaterials as those materials that are engineered with controlled release of biological stimuli. They provide the starting point for repair of diseased or damaged tissue and for protecting existing tissue. Currently, there are two general approaches to using third-generation materials. The first is \"tissue engineering,\" which involves seeding resorbable scaffolds with progenitor cells before implantation. He says it is possible to imagine in the future repairing large sections of intestinal and other soft tissue in this way. The second approach applies in situ tissue regeneration that \"involves the use of powders, solutions, or doped micro- or nanoparticles to stimulate local repair.\" DermaFuse as well as Repair and Protect fall in this category. The general idea is that the biomaterial is designed to tap into and unleash the body\'s natural genetic response. The materials, Hench says, can be tailored and graded to optimize the regeneration process. As excited as Hench is about third-generation materials, he is even more excited about the prospects of using an emerging method, fast bio-Raman spectroscopy, to provide customized treatments. He predicts that bio-Raman methods will provide \"a rapid, affordable means of diagnosis and prescription of medications, dosages, and therapies based upon specific, cell-based data of the individual patient.\" Hench says many of his views about the changes in the biomaterials landscape are contained in a major update of the book he edited in 1993, An Introduction to Bioceramics (World Scientific/Imperial College Press, Singapore), which, according to the World Scientific website has been scheduled for publication in June 2013. Meanwhile, GSK is attempting to get FDA approval to bring Repair and Protect to the US market. Although the company failed to respond to a request for an update for the toothpaste\'s approval, a source close to the product says the main obstacle is the agency\'s reluctance to permit the use of the term \"repair\" in its name and packaging. American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 33 Wound healing: An update on Mo-Sci\'s novel borate glass fibers The wound of this juvenile green sea turtle that was struck is being treated at the Georgia Sea Turtle Center, with a blend of methods that includes RediHeal brand borate glass fibers. are fairly common. Bedsores are caused by vascular degeneration that can occur after 20 minutes of constant pressure on a single skin site. The lower spine is particularly vulnerable. So, for someone who has difficulty moving, someone who is lying on his or her back for extended periods of time, bedsores are a major danger, and healing them can be a significant challenge. This gives you a sense of why we are pursuing and why there is interest in a product like DermaFuse.\" Day says that DermaFuse has a clear edge on negative-pressure healing approaches, such as a wound VAC. \"Wound VACs cost about $1,200 a week, and healing typically takes 10-12 weeks of continuous use,\" says Day. \"DermaFuse material is not going to heal you faster, but it is going to give the patient the same environment for the body to move forward. So, if you do the simple math, the DermaFuse can have the same effect and save most of the $12,000 in equipment costs.\" Jung says Mo-Sci is mainly focused on two formulations of DermaFuse: \"1550,\" which is the original composition, and \"1605,\" which has additional trace elements. He says by comparing the two they now understand more about some of the cell mechanisms that are linked to glass materials. For example, he says they have been examining the quantity of neutrophilic activity in the wound site. \"Neutrophils are subsets of the white blood cells (leukocytes), and they attack bacteria and other pathogens. In order for new tissues to grow, you have got to eliminate all of the bacteria and nonviable tissues. We have investigated and found that the 1605 composition actually will sustain 34 this neutrophilic activity for an additional week beyond ordinary DermaFuse. This is good. That means we are getting additional antimicrobial activity and cleaning the wound more aggressively,\" says Jung. says He both compositions have strong points, and their use should be patient specific. \"Although the neutrophilic activity of the 1550 drops off sooner, what we get with that is additional collagen formation. This provides the building block needed to grow new tissue. Thus, depending on the specific wound problem, the medical professionals can either focus on cleaning the wound or they can focus on healing it,\" says Jung. \"The ability to make this choice makes the material very useful.\" Jung says that with either composition, the most important test results have to do with wound vascularity or blood flow. He says, \"In wound healing comparisons, sectional images taken at 21 days show that vascularity decreases with time toward a normal line. However, our glasses keep the vascularity elevated. We think this is good because we have additional natural healing agents coming from the body. With that additional oxygen and blood flow, the waste and the CO2 can now be removed from the new cellular activity.\" Commercialization developments I discussed with Jung and Day a little bit about the medical device path to commercialization and where Mo-Sci stands. They said the company largely has been focused on protecting intellectual property and, to a large extent, gathering International Organization of Standards (ISO) 10993 biocompatibility data, a crucial step in seeking ultimate (Credit: RediHeal/Avalon Medical; Georgia Sea Turtle Center.) approval for the material from the Food and Drug Administration. In addition, they say Mo-Sci has been working on the manufacturing process, sterilization validation, and packaging. Day says they are pleased with how well things are going. \"We are probably at mid to mid-late stage of commercialization, so things are progressing very well for only having invented DermaFuse four years ago,\" he says. Day continues, “Our intellectual property claims have been filed and we already have received several of the patents we are seeking. As far as the ISO 10993 biocompatibility testing goes, these are the tests the FDA looks at for cytotoxicity, genotoxicity, sensitization, irritation, etc. The FDA wants to know if this material going to cause any harm. The good news is that independent labs have determined that our materials have passed all the ISO 10993 tests and have deemed them to be nontoxic. We feel very good about this.\" Day and Jung say another hurdle after passing the ISO 10993 requirements is that more human testing is needed. They say that additional preclinical trials are needed in other locations around the US to gather more data and examine DermaFuse performance in even more types of wounds. They say several other steps toward commercialization are in their sights. Jung says, \"Hopefully this year we will complete our FDA Master File. The Master File is an in-depth file we will provide to the FDA so the agency knows exactly how we have made and tested DermaFuse, and it is part of the typical process of commercializing a product. Ultimately, we also will prepare to engage, if necessary, in what is known as a \'pivotal human trial.\' The final step toward commercialization will be our FDA 510K submission.\" Veterinary market going well While commercialization for the human wound treatment market must await FDA approval, applications for DermaFuse in the animal care marketplace already are underway. Mo-Sci is providing DermaFuse to Maryland entrepreneur Jeff Franco. He is marketing the www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 borate glass fibers to veterinary professionals, using the RediHeal brand name, in conjunction with Avalon Medical, a larger supplier of veterinary surgical supplies. The RediHeal website (www.rediheal. com) has several examples of success with using the borate glass fibers with animals, including large and small lacerations, dental void packing, and gunshot wounds. In regard to the gunshot wound case, a dog sustained at 42-square-inch wound in its back that was treated with RediHeal. According to the company, the wound shrunk rapidly, and 40 days later it was nearly healed. In another case, RediHeal was used to heal the shell of a green sea turtle. Franco, whose background includes development of human medical devices, says he saw the relaxed veterinary regulatory environment as an opportunity and had been looking for a pioneering product. He says sales of RediHeal have been growing well, although not as fast as he thinks the glass fibers warrant. \"One of the problems is that it turns out that it is hard for vets to accept how easy it is to use RediHeal,\" Franco says with some frustration. \"Instead of just applying the pad, veterinary staff apparently first want to mix it with blood or antibiotics. Or, they want to manually debride the wound. It is just hard for them to accept that all they have to do is apply it to a wet, raw wound.\" He continues, “The education component is key. Our challenge has been getting them to understand that it is as easy as taking RediHeal out of the box, slapping it on a wound, and then covering the wound site. Our experience is that once they realize it is that simple, they gladly reuse it again.\" part Franco says that of the problem may be in how RediHeal is presented to veterinary professionals. \"I\'ve been working with the Mo-Sci staff to look at the current packaging and the form of the glass fibers. We\'ve developed a lot of good ideas, and I think the next generation of our packaging and marketing will give us a nice push. Fortunately, the product is so good, we can\'t mess it up. Once they see the results, they say, \'Holy cow,\' and they stay dedicated to the product,\" he says. While the new packaging is being finished, Franco says he is working on producing promotional videos and reaching out to groups that normally have difficult cases to treat. \"We have worked with and supplied RediHeal to vets in Africa who are trying to treat animals such as water buffalo and lions. Horses also are difficult to treat,\" says Franco. \"I\'d like RediHeal to show that it can handle the tough cases and then have it trickle down to easier ones.\" Whether it is stubborn or complicated wounds, it is hard not to imagine that Mo-Sci\'s glass fibers will weave a substantial and healthy legacy in the medical community. | october 27-31, 2013 | Palais des congrès de Montréal | Montréal, Québec, Canada save the date MS&T 13Ⓡ Materials Science & Technology 2013 Conference & Exhibition The leading forum addressing structure, properties, processing and performance across the materials community. Registration opens in June The technical program covers: • • . • Biomaterials Ceramic and Glass Materials Electronic and Magnetic Materials • Energy Issues Fundamentals and Characterization Iron and Steel • Materials-Environment Interactions • Materials Performance Nanomaterials Processing and Product Manufacturing • Special Topics www.matscitech.org Including ACerS 115th Annual Meeting The American Ceramic Society AIST ASM Everything Material. MET SOC www.ceramics.org ASSOCIATION FOR IRON & STEEL TECHNOLOGY information Society American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org CIM ICM TMS The Mala, Mulas & Mats Sock 35 36 P₂O 0.0 1.0 Metaphosphate O/P = 3.0 0.2 0.8 Pyrophosphate O/P = 3.5 Orthphosphate O/P = 4.0 0.6 0.4 0.6 0.4 Figure 1. Compositional diagram of Na₂O-FеO-Fe2O3P₂O glass studied. Glass series with constant O/P ratio (3.0, 3.1, 3.25, 3.4, 3.5, and 4.0) are represented by lines. Along each line, the O/P ratio is constant, but the Fe/P ratio changes. The black symbols indicate the analyzed compositions of the iron phosphate glasses in this work. Fe₂O₁₂+FeO 0.0 0.2 0.4 0.6 Na,O (Fe²/Fe =0.20) tot Credit: U. Ma, MS&T) he excellent chemical durability The of iron phosphate glasses makes them potential hosts to vitrify high-level nuclear waste (HLW). 1-3 The properties of iron phosphate glasses depend on glass Structural study of structure, which is determined by the type Na₂O-FeO-Fe2O3-P205 glasses by highpressure liquid chromatography and Raman spectroscopy By Lina Ma and Richard K. Brow and concentration of metal cations and the resulting phosphate chain length distributions.4-8 The structural complexity of iron phosphate glasses is increased by the variation in the Fe-redox conditions and by disproportionation reactions of phosphate anions in the melts.ª The relative fraction of Fe²+/Fe is typically about 20% for the glasses obtained by conventional melting (in air) and quenching techniques.2 2,9,10 Disproportionation reactions produce the wider distributions of phosphate chains, which are related to the glass formation energy.\' 11,12 The Flory distribution model describes the distribution of chains in phosphate melts:13 2(PC ←>>> PO3+)(n+2) (PO)(n+3) + (PO)(n+1) n+1 3n+4 n 1 3n 2 where n is the number of P-tetrahedrons in a chain. The nature of the metal cations in a phosphate glass composi tion also affects the distribution of anions in phosphate glasses. Higher-field-strength cations broaden anion distri butions, for example.\" Glass composition analysis tot (1) The average Fe²+/Fe ratio of the glasses studied here is about 0.20 ± 0.05, as determined by a titration method,¹4 and consistent with previous studies. 9,10 The sodium, iron, and phosphorus amounts were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 after dissolving glasses in sulfuric acid. Figure 1 shows the compositions of the glasses in terms of their O/P ratios. HPLC results Figure 2 shows the HPLC (high-pressure liquid chromatography) results for a series of glasses with similar Fe/P ratios, about 0.22, and increasing O/P ratios. Each peak represents one type of phosphate anion, and the size of the anion increases with the retention time. As the O/P ratio increases, the relative concentration of long phosphate chains (P > 6) decreases. When the O/P ratio reaches 3.51, the phosphate anions in the glass structure are mainly pyrophosphates (P₂, 70.7%). n In the glass series with similar O/P ratios, the replacement of sodium by iron broadens the distribution of phosphate anions. Figure 3 shows the HPLC data of glasses with O/P ratios of 3.50. Similar data were collected from glasses with O/P ratios of 3.04, 3.11, 3.26, and 3.41. Raman spectroscopic results Raman spectra of corresponding glasses were consistent with the changes in the phosphate anion distributions determined by HPLC. Figure 4 shows spectra from glasses with Fe/P = 0.22 and various O/P ratios. Figure 5 shows spectra from glasses with O/P = 3.50 and various Fe/P ratios. Using the Raman band assignments proposed by Zhang et al., as the O/P ratio increases, the frequency of the P-O stretching mode in the range 1000-1200 cm-¹ shifts to lower wavenumbers as the glass network depolymerizes. As the Fe/P ratio increases, the intensities of peaks assigned to PO3 stretching modes associated with the Q-tetrahedrons (centered near 1068 cm¹) increase. For the O/P = 3.50 series, as the Fe/P ratio increases, the Raman peaks in the range 1000-1250 cm¹ broaden and shift to higher wavenumbers. The intensity of peaks in the range of 680-760 cm-¹ assigned to the symmetric P-O-P stretching mode associated with the bridging oxygen that links neighboring tetrahedrons decreases as the Fe/P ratio increases for all glass series. Atomic units 0 5 10 15 20 25 30 0 5 10 15 0 5 O/P 3.51 3.43 3.22 3.09 3.04 10 15 20 25 Retention time (min) 30 Figure 2. HPLC chromatographs of glasses with constant Fe/P of 0.22 ± 0.01. Raman intensity O/P (Credit: U. Ma, MS&T) Atomic units سللا سد 20 20 0 5 10 15 20 20 25 25 30 Fe/P 0.67 0.59 0.48 0.39 0.34 0.23 25 30 (Credit: U. Ma, MS&T) Retention time (min) Figure 3. HPLC chromatographs of iron phosphate glasses with O/P of 3.50 ± 0.01. 1077 1250 1087 0.59 1077 1044 Fe/P 3.51 742 890 628 1197 0.67 1056 3.43 1216 1153 1081 694 3.22 1258 1171 697 1067 3.09 1296 1181 1060 704 3.04 1318 200 400 600 800 1000 1200 1400 Wavenumber (cm-1) Figure 4. Raman spectra of glasses with constant Fe/P of 0.22 ± 0.01. Quantitative analysis of HPLC HPLC provides quantitative information about the chain length distributions in a phosphate glass network because the relative area under each HPLC peak represents the relative number of PO4 tetrahedrons, n in reaction (1), in the corresponding phosphate anion. 15,16 Table I compares the average phosphate chain length (ñ )-determined (Credit: U. Ma, MS&T) Raman intensity 0.48 1067 0.39 1227 1057 0.34 1044 0.23 628 743 894 1200 200 400 600 800 1000 Wavenumber (cm-¹) 1200 1400 Figure 5. Raman spectra of iron phosphate glasses with O/P of 3.50 ± 0.01. from the HPLC data and predicted from the analyzed compositions (ICP) according to Eq 2,17 2 4. Σ[Μ]4. -[1 [P] (2) where [M] is the molar concentration of metal cation i, q, the valence of metal Table 1. Comparison of average phosphate chain length (ñ) – predicted from the analyzed compositions (ICP) with those determined from the HPLC data 3.04 ± 0.01 Fe/P HPLC ICP 0.37 3.3 28.3 0.23 3.5 26.7 0.13 7.8 32.6 3.11 ± 0.03 Fe/P HPLC ICP 0.42 3.26 ± 0.03 Fe/P 3.0 6.7 0.50 0.32 3.2 10.6 0.38 0.21 5.3 11.0 0.32 0.12 4.0 9.0 0.22 0.15 HPLC ICP 2.8 3.4 3.1 4.0 3.3 4.1 3.2 4.5 3.1 3.3 3.41 ± 0.03 Fe/P HPLC ICP 0.58 2.4 2.8 0.49 2.4 2.6 0.39 2.4 2.5 0.32 2.4 2.4 0.23 2.4 2.3 0.13 3.50 ± 0.01 Fe/P HPLC ICP 0.67 2.2 2.1 0.59 2.1 2.0 0.48 2.1 2.1 0.39 2.1 2.0 0.34 2.0 2.0 2.4 2.3 0.23 1.9 1.9 (Credit: U. Ma, MS&T) American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 37 Structural study of Na2O-FеO-Fe2O3-P205 glasses by high-pressure... cation i, and [P] the molar concentration of phosphorus. Table 1 shows that ñ calculated from relative areas in HPLC chromatographs agree well with the predicted ñ from the analyzed composi tions for glasses with larger O/P ratios (>3.3), where all phosphate anions are well resolved in HPLC. The inability to separate the chains in the P-rich glasses results in the underestimation of ñ calculated from the HPLC results. The apparent limitation of quantitative structural information to glasses with greater O/P ratios is similar to results reported in HPLC studies of zinc polyphosphate glasses, 15, 18 where good agreement in measurements of by HPLC with phosphate chain lengths predicted from equation (2) was obtained only for glasses with O/P> 3.3. Phosphate chain length distributions Introducing metal oxides into phosphate glasses produces nonbridging oxygens on the P-tetrahedrons and reduces the connectivity of the phosphate glass network. The fraction of Q¹-tetrahedrons (i is the number of bridging oxygens) is calculated from the relative area of peaks in HPLC chromatographs. Figure 6 shows one set, for glasses with a constant Fe/P ratio, plotted with solid sym50 50 PO₂ stretch (Q²) bols. 15 Corresponding Raman spectral analysis (open symbols) shows similar trends for the relative intensities for bands associated with specific Q sites. The trends in the relative intensities of the three main peaks associated with the symmetric stretching modes of Q², Q¹, and Q tetrahedrons agree well with the respective HPLC results. The pyrophosphate stoichiometry is reached when O/P = 3.5. However, HPLC and Raman spectroscopy indicate that other anions besides the pyrophosphate anion exist in these glasses. Disproportionation reactions in glassmelts explain the presence of P, and P, anions in glasses with nominal pyrophosphate compositions. Reaction (1) can be rewritten as reaction (3): 11,19 3 2P2 ← P+P 3 (3) Modeling reaction (3) as an equilibrium chemical reaction allows the calcu lation of the equilibrium constants, K₂, from the appropriate chromatographs (Figure 7). For sodium iron phosphate glasses, replacing sodium with iron promotes pyrophosphate disproportionation (K, increases). Cations with higher field strengths, as well as glasses with a greater ñ, produce wider distributions of phosphate anions.12 In their study of mixed-cation phosQ 90 80 n phate glasses, Meadowcroft et al.¹¹ found that glasses with two cations with the greatest difference between their ionic field strengths have the most negative exothermic enthalpy of mixing in glassmelts. They related this to differences in the polarization of nonbridging oxygens. They also proposed that the extent to which the values of K differ from unity may be attributed to endothermic enthalpy changes associated with the disproportionation reaction (3). Heat formation measurements have shown that glasses containing cations with lower field strengths lead to a greater enthalpy AH for each disproportionation reaction and to narrower distributions of phosphate anions.20 Sales et al.12 have shown that greater field strength cations also are associated with lower free energies of formation for their respective crystalline orthophosphates. In the present study, as Nat is replaced by Fe²* and/or Fe³* in glassmelts with a constant O/P ratio, the distribution of phosphate chains becomes broader (K2 increases), thus indicating that the AH for the endothermic disproportionation reaction decreases. Furthermore, these enthalpy changes and chain distributions may be related to glass formability. In two extreme situations, sodium pyrophosphate (66.7Na2O33.3P₂O₂) melts with narrow distributions of phosphate anions are very difficult to quench withRelative peak intensity of P-Ob stretch in Raman spectra (%) 40 50 30 20 20 PO, stretch (Q\') 10 PO stretch (Q°) 0 3.1 3.2 3.3 Q° 0 3.4 3.5 60 40 40 20 20 Q\" fraction (%) determined by HPLC Credit: U. Ma, MS&T) In(K₂) 2 -3 0 3.04 ± 0.01 3.11 ± 0.03 3.26 ± 0.03 Wavenumber (cm-1) Figure 6. Relative intensities of three Gaussian peaks used to fit the Raman spectra in the range 800-1500 cm¹ for glasses with constant Fe/P of 0.31 ± 0.01 (open symbols). The peak positions are (□) 900-960 cm³¹, (O) 1050–1070 cm³¹, and (A) 1120-1180 cm¨¹. Solid symbols are the fraction of Q\'-tetrahedra calculated from the relative area of HLPC peaks. (Lines are not fitted.) 4 3.41 ± 0.03 * 3.50 ± 0.01 0.0 0.2 0.4 0.6 Fe/(Na+Fe) ratio 0.8 1.0 Figure 7. Natural logarithm of K₂ from reaction (3) for the Na-Fe-phosphate glasses. Dashed lines are not fitted. 38 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 Ma, MS&T) out crystallization, compared with iron pyrophosphate (40Fe2O360P₂O) melts, which possess much more complex anionic structures. The effect of various valence states of iron on glass formation and chain length distribution is not clear yet. This work was supported by the Nuclear Energy University Program (US Department of Energy) under grant NEUP 09-144. Acknowledgement This work was supported by the DOE Nuclear Energy University Program under grant NEUP 09-144. References ¹B. Samuneva, P. Tzvetkova, I. Gugov, and V. Dimitrov, \"Structural studies of phosphate glasses,\" J. Mater. Sci. Lett., 15 [24] 2180-83 (1996). 2X. Yu, D.E. Day, G.J. Long, and R.K. Brow, \"Properties and structure of sodium iron phosphate glasses,\" J. Non-Cryst. Solids, 215 [21] 21-31 (1997). 3D.E. Day, Z. Wu, C.S. Ray, and P. Hrma, \"Chemically durable iron phosphate glass wasteforms,” J. Non-Cryst. Solids, 241 [1] 1-12 (1998). 4L. Zhang and R.K. Brow, \"A Raman study of iron phosphate crystalline compounds and glasses,” J. Am. Ceram. Soc., 94 [9] 3123-30 (2011). 5A.C. Wright, R.N. Sinclair, J.L. Shaw, R. Haworth, G.K. Marasinghe, and D.E. Day, “A neutron diffraction study of the structure of iron phosphate glasses,\" Phys. Chem. Glasses: B, 49 [1] 1-7 (2008). 6C.H. Booth, P.G. Allen, J.J. Bucher, N.M. Edelstein, D.K. Shuh, G.K. Marasinghe, M. Karabulut, C.S. Ray, and D.E. Day, \"Oxygen and phosphorus coordination around iron in crystalline ferric ferrous pyrophosphate and iron phosphate glasses with UO2 or Na₂O,” J. Mater. Res., 14 [6] 2628-39 (1999). \'P.A. Bingham, R.J. Hand, O.M. Hannant, S.D. Forder, and S.H. Kilcoyne, “Effects of modifier additions on the thermal properties, chemical durability, oxidation state, and structure of iron phosphate glasses,\" J. Non-Cryst. Solids, 355, 1526-38 (2009). 8B. Al-Hasni and G. Mountjoy, \"Structural investigation of iron phosphate glasses using molecular dynamics simulation,\" J. Non-Cryst. Solids, 357, 2775-79 (2011). ⁹G.K. Marasinghe, M. Karabulut, C.S. Ray, D.E. Day, M.G. Shumsky, W.B. Yelon, C.H. Booth, P.G. Allen, and D.K. Shuh, \"Structural features of iron phosphate glasses,\" J. Non-Cryst. Solids, 222, 144-52 (1997). 10H. Akamatsu, S. Oku, K. Fujita, S. Murai, and K. Tanaka, “Magnetic properties of mixed-valence iron phosphate glasses,\" Phys. Rev. B, 80, 134408 (2009). T.R. Meadowcroft and F.D. Richardson, \"Structural and thermodynamic aspects of phosphate glasses,\" Trans. Faraday Soc., 61, 54-70 (1965). 12B.C. Sales, L.A. Boatner, and J.O. Ramey, \"Intermediate-range order in simple metal phosphate glasses: The effect of metal cations on the phosphateanion distribution,\" J. Non-Cryst. Solids, 232-234, 107-12 (1998). 13P.J. Flory, \"Random reorganization of molecular weight distribution in linear condensation polymers,\" J. Am. Chem. Soc., 64 [9] 2205-12 (1942). 14S.I. Grishin and O.H. Tuovinen, \"Fast kinetics of Fe2+ oxidation in packed-bed reactors,” Appl. Environ. Microbiol., 54 [12] 3101-106 (1988). 15B.C. Sales, L.A. Boatner, and J.O. Ramey, \"Chromatographic studies of the structures of amorphous phosphates: A review,\" J. Non-Cryst. Solids, 263-264, 155-66 (2000). 16B.C. Sales, J.U. Otaigbe, G.H. Beall, L.A. Boatner, and J.O. Ramey, \"Structure of zinc polyphosphate glasses,\" J. Non-Cryst. Solids, 226, 287-93 (1998). 17B.C. Sales, R.S. Ramsey, J.B. Bates, and L.A. Boatner, \"Investigation of the structural properties of lead iron phosphate glasses using liquid chromatography and Raman scattering spectroscopy,\" J. Non-Cryst. Solids, 87, 137-58 (1986). 18B. Tischendorf, J.U. Otaigbe, J.W. Wiench, M. Pruski, and B.C. Sales, \"A study of short and intermediate range order in zinc phosphate glasses,\" J. NonCryst. Solids, 282, 147-58 (2001). 19J.R. Van Wazer, Phosphorus and its compounds. Interscience, N.Y., 1958. 20T.R. Meadowcraft and F.D. Richardson, \"Heats of formation of some crystalline and glassy phosphates,\" Trans. Faraday Soc., 59, 1564-1571 (1963). January 22-24 DoubleTree by Hilton Orlando at Sea World® | Orlando, Fla., USA ELECTRONIC MATERIALS AND APPLICATIONS 2014 Call For Papers The American Ceramic Society www.ceramics.org Abstracts due September 12, 2013 www.ceramics.org/ema2014 American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 39 rilem materials and structures matériaux et constructions research and testing/essais et recherches septembre-octobre 1985 n° 107 Dunod Cover of journal in which \"Le beton numerique\" was published. The cover shows the 2D finite-element mesh incorporating the circular sand and gravel particles. The computational materials science 40 40 he development of my career parThe allels the historical growth of the computational materials science of concrete. Thus, my hope is that my personal point of view might help some of the younger ACerS members see how a career can develop (mostly unplanned). In addition, I believe the facts of history can be much more stimulating when acquired in a biographical context, another reason for the added personal touch. From its humble beginnings back in the 1960s, computational materials science has come a long way. The field currently is getting even more exciting with ideas like integrated computational materials engineering¹ being seriously considered in the beginning of national programs like the Materials Genome Initiative. Of course, the development of computational materials science, in general, has gone hand-in-hand with the startling increases in computer processing speed and memory over the same time period. The computational materials science of concrete is no different. With this type of work now firmly established for cement and concrete, this seems like a good time to examine the origins of this field from a viewpoint-possibly a bit distorted by looking through my personal lens-and to delineate where it needs to go in the future, with, I hope, a more objective vision. of concrete: My background Past, present and future By Edward J. Garboczi Computational materials science of concrete is now a viable discipline that bridges the gap between fundamental principles and practical applications. In 1985, I earned a PhD in condensed matter physics from Michigan State University, with a thesis on computer simulation models of the elastic properties of amorphous semiconductors. That was 27 years ago, but my thesis work exemplifies the rapid development of computers since then. For example, to finish up my thesis research, I tied up the Michigan State University mainframe computer-all two megabytes of its RAM-for several weeks! My thesis advisor was Michael Thorpe, and, in subsequent years, I have told him that I am still doing random condensed matter physics, but just at a different length scale! From 1985 to 1988, Armstrong World Industries in Lancaster, Pa., employed me to work on calcium phosphate cements for inorganic ceiling boards, and I began learning a magic word: \"microstructure.\" At Armstrong, we were attempting to develop a macro-defect-free (MDF) twin-roll process for our patented inorganic cement. In this pursuit, I studied the MDF literature of the 1970s and 1980s and was eventually led to a special 1983 issue of the Philosophical Transactions of the www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 Royal Society of London journal devoted to new developments in cements for the 1990s.3 Reading this issue fired my interest in cement and concrete in general, and I moved to NIST in 1988, replacing my friend Hamlin Jennings who had left in 1987 for Northwestern University. At NIST, my division chief was visionary scientist and research leader Geoffrey Frohnsdorff (1928-2006), who had a key article in that 1983 issue.4 Frohnsdorff cofounded the ACerS Cements Division, one of his many accomplishments that have helped our field tremendously. He was a modest man, who, at his retirement, said that his career had consisted of \"two or three good ideas and the rest of the time spent signing bits of paper.\" One of his good ideas was, in 1968, developing, programming, and publishing the first computer model of cement hydration.\" ... Model building Although it was not as clear to me at the beginning as it would be later, my long-term goal at NIST was to make the computational materials science of concrete a viable discipline, one that could work with experiment as an equal partner to solve the hard problems posed by this complex, random, multiscale material. Several physicist friends told me, \"Physicists do not work on messy problems like concrete.\" Civil engineering workers told me that fancy models were not going to be useful to \"the average concrete worker.\" But, I was open to the idea of going against “common-sense\" because Albert Einstein, one of my heroes, said, \"Common-sense is (only) the collection of prejudices acquired by age eighteen.\" I wanted to break through the common-sense prejudices about concrete that were then current among most materials scientists. I explicitly went to NIST, at first, to further develop a 3D cement-paste microstructural model that Jennings and Johnson were the first to create in 1986. This model approximately handled processing (e.g., cement hydration) and microstructure, and, thus, had two of the three components of the classic processing-microstructure-properties triad. However, I quickly realized that there was a major limitation on the model\'s future usefulness: It would be very difficult to compute material properties based on how it stored the model\'s microstructure, viz., an approach based on centers and radii of spherical particles in a virtual container. I needed to get this property computation part operational. Without that component, the model could not be truly called a materials science model, and its results could not be directly compared with experiment. Illustration of 2D cross section of the Jennings-Johnson 1986 cement paste model. To put the properties issue in context, one of the difficult problems in the field that spurred this model development was the need to understand concrete durability. Because controlled degradation experiments typically took decades (and even accelerated experiments could take months), an accurate microstructure development-property model would enable virtual experiments to be run in much shorter times. A second hard problem was material optimization. Concrete has many possible components, and it is a massive job to attempt experimentally to optimize among them. An accurate model would do this much faster. Four sources helped inspire my ideas about how to calculate properties based on microstructure, which ultimately led to a new type of model. The first source was the field of my PhD work, amorphous semiconductors. Researchers in the 1960s had developed computational models of atoms, randomly linked together to simulate the structure of these materials, on which to calculate properties and give computer-based theoretical predictions to guide and interpret experiments. The second intellectual source was \"Le béton numerique,\" by Roelfstra, Sadouki, and Wittmann. They developed a simple 2D model of concrete structure, which was then \"wired up\" with a finite-element mesh to predict properties. American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org The third intellectual source was an algorithm, developed by my friend Larry Schwartz at Schlumberger,8 that used the random trajectories (random walks) of mathematical points in a pore space to compute the diffusivity of a porous material for a Jennings-Johnson spheres-in-a box type of model. My fourth source came from what I learned with my colleague Dale Bentz about representing microstructure information, whether from a model or from some type of microscope or camera, in a digital image format. Combining the idea of random walks, digital images, and property calculations led Dale and me to a new type of cement paste model whose random digital structure was built up by random walks of various chemical phases. The digital image format breakthrough was the last piece needed for the ability to compute any property via finitedifference and finite-element algorithms, based on the 3D digital lattice structure, although with some restrictions on microstructure length scales. I concentrated on developing new algorithms explicitly written for property computation in digital image models, while Dale worked on further developing the cement paste microstructure model, soon to be called CEMHYD3D. Realistic (complex) cement mineralogy was added with the help of Paul Stutzman. The support of 41 (Credit: Jennings and Johnson; Journal of the American Ceramic Society) The computational materials science of concrete: Past, present and future VCCTL/CEMHYD3D cement paste model-before hydration (showing multiphasic cement particles) and after hydration (showing the many new phases and remnants of the old phases). and collaboration with the National Science Foundation (NSF) Center for Advanced Cement-Based Materials (ACBM), headquartered at Northwestern University, also was very important to this effort in the 1990s. The combination of these four ideas led to what truly could be called a computational materials science model. Around 1990, I started using the actual term \"computational materials science of concrete.\" Practically speaking, concrete is a multiscale material with random structure from the nanometer to the centimeter and beyond. Given this, I next wanted to move into concrete-length scales so that the term \"computational materials science of concrete\" could be used more truthfully. To do this, we first used spheres as simple models of aggregates, such as sand and gravel, packed into a cement paste matrix. We later developed 3D models of real-shaped sand and gravel, based on X-ray computed tomography, which brought more accuracy to our concrete models. (These random shape measurement and mathematical procedures also are used to analyze other particulate materials outside the concrete world, including simulated lunar soil, shredded tires for waste treatment systems, breast cancer tumors, crushed waste glass, chemical explosives, and metal powders for additive manufacturing.) Aside on simple vs complex models We now have most of these models integrated into the VCCTL-Virtual 42 Cement and Concrete Testing Laboratory-that covers the micrometer to millimeter length scale of concrete. Companies are starting to have success using this computational materials science code to guide and replace some of their testing. Because the VCCTL is a \"desktop computing\" software package, some of our more complicated models that require much more computer power cannot be part of it. But, the VCCTL becomes more effective with more desktop computing power and, of course, that is constantly improving. There is one continuing argument about the computational materials science of concrete that occurred at the beginning of the field and unfortunately continues today. Basically, the experimentalists and industrial workers want models that run quickly on a desktop computer. On the other hand, theorists want to use powerful, more complex and realistic models, requiring parallel supercomputers that can handle the fundamental chemistry and physics of cement-based materials. My view is that this is an artificial competition and unfortunately often involves disparaging the one by insisting that the other is the only valid approach. Indeed, there is a difference between models that daily can help experimentalists and industry, and models that help us understand complex, fundamental issues. The correct way to link the two is to build simple, valid, nonfitting models that can run on desktop computers that are abstractions from validated, realistic, complex models that are run on parallel supercomputers. Unfortunately, at least in the concrete world, simple models are often used that have not been linked to more complex and realistic models. As Einstein also said, \"Everything should be made as simple as possible, but not simpler.” One use for the computational materials science of concrete is to solve problems accurately and to validate and improve the simpler models in everyday use in the cement and concrete world. Encouraging signs Currently, various signs suggest that the computational materials science of concrete field is fairly healthy. There is now much more acceptance in academia and industry of this endeavor than there was 20 years ago. What has caused this sea change? Clearly, we can attribute it to success in solving real problems and accurate comparisons to real experiments. In addition, the educational component has been crucial. The annual threeday ACBM-NIST Computer Modeling Workshop has taught the rudiments of the computational materials science of concrete to more than 600 people since its beginning in 1990, and the NIST Educational Monograph (\"An electronic monograph: Modeling and measuring the structure and properties of cementbased materials,\" see http://concrete. nist.gov/monograph), begun in 1997, has educated thousands more across the world in these topics. The influence of the Monograph is reflected in the metric that between 6,000 and 10,000 independent IP addresses currently access it each month. As a reviewer for and reader of journals, I find much more computational work now than in the past, in the United States, Europe, and Asia. I even find civil engineers doing molecular dynamics, a practice that 20 years ago I never expected to happen in my lifetime. Computer power continues to increase rapidly with parallel processing and graphical processing units (GPUs). As always, progress in this field goes hand in hand with progress in computer hardware and software. For cement-based materials like concrete, the www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 Figure X. As this image shows, computing the transport through the cement paste surrounding the aggregates is a difficult problem. In the image, the model aggregate has been rendered transparent, so that only the cement paste matrix is seen. NSF explicitly has been calling for combined experimental and computational approaches. Molecular- and nanometerscale models are starting to be generated at many institutions. For example, a large center for this type of modeling is at the Massachusetts Institute of Technology, where work is funded by members of the cement and concrete industry. This type of support is very encouraging. So, for the first time, we have the opportunity to start assembling a multiscale suite of models, version 1.0, because concrete, as I have said before, is really a multiscale material. There will be many gaps, but it is good to identify the gaps so we know where to focus future attention. In the world of materials, in general, ideas such as Integrated Computational Materials Engineering (ICME), advanced by the National Academy of Science, are taking hold. ICME-the idea that experiments should be performed together with realistic computational models—is the intellectual driving force behind the Materials Genome Initiative (MGI), which can be summarized as \"new materials by computational design.\" Where do we go from here? The goal of MGI, an initiative closely related to manufacturing, is to accelerate materials design via computation enabled by data repositories, models, and information transfer links. There is (Credit: NIST Online Monograph of Cement-based Materials.) a large opportunity for concrete in this approach-if we can take the models to the next step to make them more suitable for design. The current elaboration of the computational materials science of concrete is based on the experimental knowledge gleaned over the past 50 years. Although this has been very beneficial, we are using up our “seed corn.\" Our models cannot progress further without a new influx of experiments. There are many materials design problems, such as finding the best composition for concrete for a specific geographic region and application, that our computational materials science models cannot handle, and will not be able to handle without the input of new fundamental measurements. The new measurements needed mainly involve knowledge of the basic hydration reactions, thermodynamics, dissolution of cement minerals, and nucleation and growth mechanisms for each hydration product. 10 The heart of the computational materials science of concrete is building cement paste microstructure (and nanostructure) by simultaneously modeling chemistry and the growth of structure, i.e., the formation of microstructure via chemical reaction. Adding sand and gravel, although a complicated composite problem, remains only a composite problem that we generally have learned how to tackle. But, what we do not know about hydration could fill a book. Admittedly, other types of measurements are needed, including controlled fracture and viscoelastic measurements as well as the basic chemistry and physics of degradation. These also will support model growth, but the hydration-related measurements that I discuss below are more fundamental and, therefore, should have priority. The basic hydration reactions involving portland cement and water are known only in a broad form, and much less is known about reactions involving widely used byproducts, such as fly ash and blast furnace slag. Details of what phases form in solution and the ratecontrolling mechanisms and their associated rate constants are not well-known, at least not well enough for sophisticated hydration models, such as HydratiCA,11 American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org Figure X. This image shows a simple concrete microstructure, including only the larger aggregates, created using a recent model developed by workers and Delft and the author. to be able to function as a design tool for new cement-based materials that incorporate industrial byproducts. Portland cement is made up of many mineral phases, most of which dissolve in water and most of which contain impurities that can affect the mechanisms and rates of hydration reactions of their own and those of other minerals. The solubility limits of known impurities in cement minerals and hydration products are not known, and accurate models of the activity of solute components at the high ionic strengths commonly found in cement-based binders are not available. For the dissolution of each cement mineral, the rate of pure dissolution in isolation as a function of composition, temperature, and undersaturation needs to be measured. With these data in hand as a reference, the influences of other important solute ions, such as sulfates and aluminates, can be isolated and measured to determine unequivocally the interactions among cement phases. The nucleation rates for hydration products, as functions of solution composition and temperature, are not known. The actual nucleation mode in the presence of various surfaces needs to be determined. For heterogeneous nucleation, the strength of adhesion of a product to mineral surfaces and the ability of products to affect further dissolution of covered mineral surfaces are not known. 43 (Credit: Z. Qian, E. Schlangen, G. Ye, and E.J. Garboczi, unpublished.) The computational materials science of concrete: Past, present and future Finally, the rate of pure hydration product growth in supersaturated solutions, as a function of temperature and supersaturation degree, needs to be measured. The rate of uptake of various solution impurities in hydration products also needs to be determined. Likewise, the effect on the phase growth rate because of impurity uptake is not presently known. These fundamental building blocks will provide the basic thermodynamic and kinetic foundations that HydratiCA and other realistic models need to advance to the next level of materials design. Prospectus and need for a data repository The properties listed above can be measured using sophisticated techniques developed in the past 20 years, with some adaptation. But, it will take a lot of work to get these measurements done. As these data are gathered, once and for all, this information should be put into a cement materials thermokinetic data repository (that NIST would be happy to host on its servers). Validated experimental data as well as data from molecular scale models from all over the world could feed into it. To make effective use of this data repository, the cement and concrete community will be pushed toward better material characPublicly available modeling programs through NIST • Virtual Cement and Concrete Testing Laboratory • Computation of Water-to-Cement Distance Function - for computing the water-to-cement distance (proximity) function • Stokes Three-Dimensional Permeability Solver - for the computation of the permeability of any digitized porous microstructure Internal Curing with Lightweight Aggregates ― models and publications concerned with mixture proportioning and other aspects of internal curing • Concrete Optimization Software Tool (COST) - for optimizing concrete mixture proportions based on response surface methodology experimental design principles and statistical analysis • A Prototype Service Life Prediction Program - for service life prediction of steel-reinforced concrete exposed to chloride ions • CEMHYD3D Computer Program 44 44 terization. This effort needs long-term, sustained, coordinated support. The funding sources will have to be patient. \"People love chopping wood. In this activity one immediately sees results,\" said Einstein. But these measurements are not just chopping wood, because once they are done, they are done! This data repository will be incredibly useful-but in what ways? Undoubtedly, the new data will enable the further development and successful use of precise, comprehensive models. These models then will be able to accurately • Predict time-dependent properties; • Predict the effect of new chemistries (e.g., oil well cements, calcium sulfoaluminate cements); • Predict the influence of existing chemical admixtures; and Inspire new chemical admixtures by running models to show the possible effects of changes in mechanisms. If new supplementary cementitious materials (such as fly ash, slag, limestone, rice hull ash, expanded clays, waste glass, and recycled concrete) are controlled by the same types of phases and chemistry, then these models also will be able to accurately incorporate the use of these materials. If not, more measurements will need to be made, using techniques that were developed for cement. The same can be said for degradation reac- 3D cement hydration and microstructure development modeling ⚫HCSSMODEL Computer Program - 3D concrete microstructure modeling • Finite element/finite difference programs - for computing the linear elastic and linear electric properties of digital images in 2D and 3D • 4SIGHT Computer Program - for concrete performance prediction under various exposure conditions • CONCLIFE Computer Program - for estimating the service life of concrete pavements and bridge decks exposed to sulfate attack and freeze-thaw deterioration • SULFATE2 Computer Program - for computing the resistance of concrete to sulfate attack • Cement Hydration Modeling - for modeling cement hydration and percolation processes For more information, see: http://ciks.cbt.nist.gov/ ~bentz/phpct/cmml.html tions: If the same type of necessary fundamental measurements are made, they will enable the development of accurate degradation models, thus enabling service life prediction. The latter is a particularly important issue when considering infrastructure renewal decisions. If we can develop this data repository, the computational materials science of concrete truly can become multiscale and reach the higher level needed to become a paradigm of the ICME and the MGI approach. Industry, then, would be able to engineer concrete for any application and make effective use of a wide range of component materials. For a large concrete construction job, given a range of local materials as well as environmental conditions and structural requirements, these models will show how to select and best use the available materials to achieve job specifications. Final personal thoughts I have enjoyed attempting to bring comprehension to my own little part of concrete research, which itself is a very small part of all scientific endeavor. I have received a great deal of help along the way. Let me start my thanks with Einstein by quoting him one last time: \"The most incomprehensible thing about the world is that it is comprehensible.\" Despite his matchless achievements as a physicist (and his remarkable quotability), I will venture to differ with him about incomprehensibility. I believe, “in the beginning, God created the heavens and the earth\"--we were created in his image, so that is why the world, also his creation, is, in general, comprehensible to us. I am grateful for this basis of meaning and enjoyment for my pursuit of science. I would like to especially thank my PhD thesis advisor, Mike Thorpe, and NIST colleagues Jeff Bullard, Dale Bentz, Paul Stutzman, Clarissa Ferraris, Nicos Martys, Ken Snyder, Jack Douglas, Geoff Frohnsdorff, and Jim Clifton. My principal colleagues at ACBM were Suru Shah, Francis Young, Tom Mason, and Hamlin Jennings. ACBM and NIST have played crucial roles in the development of my career and in the development of the computational materials science of concrete. www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 Garboczi. About the author Edward J. Garboczi works in the Engineering Laboratory, Materials and Structural Systems Division, of the National Institute of Standards and Technology, Gaithersburg, Md. Editor\'s note This article has been adapted from the 2012 Della Roy Lecture, given June 11, 2012, at the annual meeting of the ACerS Cements Division, University of Texas-Austin. References \'http://www.nap.edu/openbook.php?record_ id=12199 http://www.whitehouse.gov/mgi 3Technology in the 1990s: Developments in the science and technology of hydraulic cements, Edited by P. Hirsch, J.D. Birchall, D.D. Double, A. Kelly, G.K. Moir, and C.D. Pomeroy, Philos. Trans. R. Soc. London A, 310 [1511] 1-207 (1983). 4G. Frohnsdorff and J. Skalny, \"Cement in the 1990s: Challenges and opportunities,\" Philos. Trans. R. Soc. London A, 310 [1511] 17-30 (1983). 5G. Frohnsdorff, W.G. Fryer, and P.D. Johnson, \"The mathematical simulation of chemical, physical, and mechanical changes accompanying the hydration of cement\"; Supplementary Paper II-44 presented at the 5th International Symposium of the Chemistry of Cement, Tokyo, 1968. 6H.M. Jennings and S.K. Johnson, “Simulation of microstructure development during the hydration of a cement compound,” J. Am. Ceram. Soc., 69, 790-95 (1986). 7P.E. Roelfstra, H. Sadouki, and F.H. Wittmann, \"Le béton numerique,\" Mater. Struct., 18 [107] 327-35 (1985). 8L.M. Schwartz and J.R. Banavar, \"Calculation of electrical transport in continuum systems by diffusion simulation,\" Physica A: Statistical Mechanics and its Applications, 157 [1] 230-34 (1989). \'D.P. Bentz, \"Three-dimensional computer simulation of portland cement hydration and microstructure development,\" J. Am. Ceram. Soc., 80 [1] 3-21 (1997). 10(a)J. W. Bullard, H.M. Jennings, R.A. Livingston, A. Nonat, G.W. Scherer, J.S. Schweitzer, K.L. Scrivener, and J.J. Thomas, \"Mechanisms of cement hydration,\" Cem. Concr. Res., 41 [12] 1208-23 (2011). (b)H.M. Jennings and J.W. Bullard, “From electrons to infrastructure: Engineering concrete from the bottom up,\" Cem. Concr. Res., 41 [7] 727-35 (2011). \"J.W. Bullard, \"A determination of hydration mechanisms for tricalcium silicate using a kinetic cellular automaton model,” J. Am. Ceram. Soc., 91 [7] 2088-97 (2008). PRAGUE ICG 2013 www.icg2013prague.cz The 23rd International Congress on Glass Prague, Czech Republic (Europe), July 1 - 5, 2013 This triennial event, organised by the International Commission on Glass (ICG) will bring together key players in glass science, technology and production: glass manufacturers, providers, researchers, engineers and students for a series of conferences covering most aspects related to the vitreous state and glass material science. Topics Theory of Glass, Glass Modelling, Glass Transitions, Relaxation of Glass, Glass Surfaces, Glass Chemical Durability and Safety of Nuclear Power Plant, Thermodynamics of Glass, Other Glass Properties, Mechanical Properties, Glass & Vibrations, Crystallization, Non-oxide Glass, Optically Active Glass, Glass Formation, Sol-gel, New Glasses, Bio-glasses, Environmental Issues, Glass Melting and Forming, Raw Materials & Refractories Invited speakers David Pye (USA) - “Glass and the Nanotechnology Paradigm\" and Beerkens R. (Netherland), Deubener J. (Germany), Ferrari M. (Italy), Girold Ch. (France), Heo J. (South Korea), Liška M. (Slovakia), Němec L. (Czech Republic), Ojovan M.I. (UK), Pascual M.J. (Spain), Richardson K. (USA), Richter R. (Germany), Rouxel T. (France), Salmon P. (UK), Sierka M. (Germany), Sundaram S.K. (USA), Tatsumisago M. (Japan), Zwanziger J. (Canada) Congress Secretariat ICARIS Conference Management, Czech Republic Contact: Romana Kočová (Romana@icaris.cz) American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 45 A World of Science The 10th Pacific Rim Conference on and PACRIMO Ceramic and Glass Technology Technology PACRIMIO Including GOMD 2013 - Glass & Optical Materials Division Annual Meeting June 2–7, 2013 | Hotel Del Coronado | San Diego, Calif., USA CRIM10 is designed for materials scientists, engineers, researchers, and manufacturers. It will deliver the opportunity to share knowledge and state-of-the-art advancements in materials technology. The PACRIM 10 technical program covers a variety of topics that identify global challenges and opportunities for various ceramic and glass technologies. The program fosters discussions on the future of specific fields on a global scale. It delivers a forum for knowledge exchange and facilitates new contacts from around the world. Register at www.ceramics.org/pacrim10 to participate in this critical global event. Endorsed by: The Chinese Ceramic Society The Korean Ceramic Society The Ceramic Society of Japan The Australian Ceramic Society The Indian Ceramic Society World Academy of Ceramics The Brazilian Ceramic Society The Thai Ceramics Society The European Ceramic Society Mexican Society of Materials PACRIM 10 Program Chair Sponsors H.T. Lin Oak Ridge National Laboratory Oak Ridge, Tenn., USA CCTC CORNING 三环集团 Since 1928 SICCAS 中国科学院上海硅酸盐研究所 JOURNAL OF NON-CRYSTALLINE SOLIDS UBE UBE INDUSTRIES.LTD. DUCK SEONG GREEN HC TECH CO LTD Environment Technology Battelle The Business of Innovation STEAN POLYTECHNICAL 1038 &GENIATECH http://www.geniatech21.com INTERNATIONAL JOURNAL OF Applied Glass SCIENCE 46 46 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 The American Ceramic www.ceramics.org Short Courses Register now at www.ceramics.org/pacrim10 Sintering of Ceramics* Instructor: Mohamed N. Rahaman, Missouri University of Science and Technology Fundamentals of Glass Science and Technology* Instructor: Arun K. Varshneya, Alfred University Rates: ACerS Member - $945 Student - $420 *Separate registration fee required. Nonmember $1,035 Course plus Membership - $1,065 Schedule of Events Saturday, June 1 Sintering of Ceramics Short Course Sunday, June 2 8:30 a.m.-5:30 p.m. Sintering of Ceramics Short Course 8:30 a.m.-4:30 p.m. Registration & Tabletops Welcome Reception Monday, June 3 Registration & Tabletops PACRIM Opening Remarks & Plenary Lunch on Own Optional Tours Balboa Park The 1,200-acre park is home to 15 museums as well as recreational and cultural facilities, including the Aerospace Museum and the San Diego Museum of Art. San Diego Zoo The 100-acre zoo is a sanctuary for more than 4,000 animals and houses and more than 6,500 plant species. Wednesday, June 5, 1:00 p.m. – 5:00 p.m. To sign up, visit www.ceramics.org/pacrim10 Tabletops LAEIS GmbH Empower Materials Pred Materials International Inc. NETZSCH Instruments North America LLC Olympus Wiley 3:00 p.m.-7:00 p.m. 5:00 p.m. 7:00 p.m. 7:30a.m.-6:00 p.m. 8:45 a.m. 12:10 p.m. 12:10 p.m.-1:20 p.m. Varshneya Frontiers of Glass Science Lecture 1:00 p.m. – 1:50 p.m. Concurrent Technical Sessions GOMD Business Meeting Student Career Roundtable Tuesday, June 4 Registration & Tabletops George W. Morey Award Lecture Concurrent Technical Sessions Lunch on Own Norbert J. Kreidl Award Lecture Concurrent Technical Sessions Poster Session Set Up Poster Session Wednesday, June 5 Registration & Tabletops Concurrent Technical Sessions Free Afternoon Fundamentals of Glass Science Short Course Thursday, June 6 Registration & Tabletops Stookey Lecture of Discovery Concurrent Technical Sessions Fundamentals of Glass Science Short Course Lunch on Own Concurrent Technical Sessions Conference Dinner Friday, June 7 Registration & Tabletops Concurrent Technical Sessions 1:20 p.m.- 6:00 p.m. 6:00 p.m. 7:00 p.m. 6:00 p.m.-7:00 p.m. 7:30 a.m.-6:00 p.m. 8:00 a.m. 8:30 a.m. Noon Noon–1:20 p.m. 8:50 a.m. 1:00 p.m.-1:50 p.m. 1:20 p.m.- 6:00 p.m. 2:00 p.m.-5:00 p.m. 5:30 p.m. 8:00 p.m. 7:30 a.m. 12:30 p.m. 8:30 a.m. Noon 1:00 p.m.-5:30 p.m. 8:00 a.m.-6:00 p.m. 8:00 a.m. 8:50 a.m. 8:30 a.m. Noon 8:30 a.m.-4:30 p.m. Noon 1:20 p.m. 1:20 p.m.- 6:00 p.m. 7:00 p.m. 9:30 p.m. 8:00 a.m. Noon 8:30 a.m. Noon Hockmeyer Equipment Co. Hotel Del Coronado 1500 Orange Ave., Coronado, CA 92118 (near San Diego) Phone: 800-468-3533 | Phone: 619-435-6611 Contact the hotel directly to make reservations. The rich 125-year history of the Del includes international dignitaries, Hollywood starlets, and even a ghost. American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 47 48 48 World of Science A www.ceramics.org/pacrim10 June 2-7, 2013 | Hotel Del Coronado | San Diego, Calif., USA PACRIMO and Technology The 10th Pacific Rim Conference on Ceramic and Glass Technology Including GOMD 2013 - Glass & Optical Materials Division Annual Meeting PACRIM 10 Plenary Speakers Jeff Wadsworth President & CEO of Battelle Memorial Institute, USA The evolving R&D model: Driving energy transformation through advances in materials science Stookey Lecture of Discovery G. Clinton Shay Retired, Corning Incorporated The torturous path of the fusion sheet process development Hong-Kyu Park Fellow of LG Chem Battery R&D, Korea Technology trend in lithium-ion battery for electric vehicle and energy storage system application George W. Morey Award Lecture Denise Krol University of California, Davis Focus and Flash! Changing the structure of glass with light Tomoyoshi Motohiro Toyota Central R&D, Japan Research activities for future challenges in global energy and environment in TCRDL Stephen Elliott Cambridge University, UK Elliott will deliver his Lecture at GOMD 2014 in Aachen, Germany. The title will be announced later. M.K. Badrinarayan VP & Research Director, Inorganic and Broad-Based Technologies, Corning Incorporated, USA Glass and ceramics for energy applications Darshana and Arun Varshneya Frontiers of Glass Science Lecture Opening lecture for the Glass & Optical Materials Division program. Walter Kob Full Professor, Department of Physics, University of Montpellier, France The properties of glassforming systems at the Kauzmann temperature Norbert J. Kreidl Award for Young Scholars Lina Ma Missouri University of Science and Technology Structural study of Na₂O-FeO-Fe2O3-P₂O, glasses by high-pressure liquid chromatography and Raman spectroscopy GOMD 2013 Award Sponsors CORNING SCHOTT PPG Coe College www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 SYMPOSIA SCHEDULE Sessions Date Time Location 2ND INTERNATIONAL RICHARD M. FULRATH SYMPOSIUM ON \'FRONTIERS OF CERAMICS FOR SUSTAINABLE DEVELOPMENT\' Ceramics for Sustainable Development I Ceramics for Sustainable Development II Monday, June 3 Tuesday, June 4 1:20 p.m. 5:30 p.m. Crown 8:30 a.m. Noon Crown Ceramics for Sustainable Development III Ceramics for Sustainable Development IV Tuesday, June 4 Wednesday, June 5 1:20 p.m. 5:10 p.m. Crown 8:30 a.m. 11:30 a.m. Crown S1: ADVANCED CHARACTERIZATION AND MODELING OF CERAMIC INTERFACES Modeling and Control of Ceramic Interfaces Monday, June 3 1:20 p.m. 5:40 p.m. Continental Advanced Characterization of Ceramic Interfaces Tuesday, June 4 8:30 a.m. Noon Continental Interface Structures and Properties in Ferroic Materials Tuesday, June 4 1:20 p.m. 5:10 p.m. Continental Advanced Theoretical Modeling of Ceramic Interfaces Wednesday, June 5 8:30 a.m. 12:10 p.m. Continental S2: CERAMICS BY GENOME Functional Ceramics Thursday, June 6 8:30 a.m. 10:20 a.m. Continental Structural Ceramics Methods in Genome-Related Research Surfaces, Interfaces, and Glasses Spectroscopy and Other Approaches in Genome Research Energy and Bioceramics Thursday, June 6 10:20 a.m. Noon Continental Thursday, June 6 1:20 p.m. 3:40 p.m. Continental Thursday, June 6 3:40 p.m. 5:30 p.m. Continental Friday, June 7 8:30 a.m. 10:20 a.m. Continental Friday, June 7 10:20 a.m. 11:10 a.m. Continental S3: NOVEL, GREEN, AND STRATEGIC PROCESSING AND MANUFACTURING TECHNOLOGIES Advanced Composite and Hybrid Processes Thursday, June 6 8:30 a.m. 12:10 p.m. Hanover Chemistry of PDCS Modeling and Nanostructure of PDCS Energy and Functional Applications I Energy and Functional Applications II Processing of PDCs: Coatings Processing of PDCs: Porous Ceramics and Membranes | Processing of PDCs: Porous Ceramics and Membranes II Processing of PDCs: Fibers Design-Oriented Manufacturing and Processing Novel Synthesis and Processing S4: POLYMER-DERIVED CERAMICS AND COMPOSITES Chemistry and Thermodynamics of PDCS Thursday, June 6 1:20 p.m. 6:00 p.m. Hanover Friday, June 7 8:30 a.m. 11:50 a.m. Hanover Monday, June 3 1:20 p.m. 3:40 p.m. Garden Monday, June 3 3:40 p.m. 6:00 p.m. Garden Tuesday, June 4 8:30 a.m. 10:10 a.m. Garden Tuesday, June 4 10:10 a.m. Noon Garden Tuesday, June 4 1:20 p.m. 3:30 p.m. Garden Tuesday, June 4 3:30 p.m. 6:00 p.m. Garden Wednesday, June 5 8:20 a.m. 10:20 a.m. Garden Wednesday, June 5 10:20 a.m. 12: 10 p.m. Garden Thursday, June 6 8:30 a.m. 10:30 a.m. Garden Processing of PDCs: Composites and Nanocomposites I Processing of PDCs: Composites and Nanocomposites II Composite Structure Control by Powder Processing Advanced Powder Processing for Functional Ceramics Nano/Microstructure Control by Powder Processing I Advanced Powder Processing for Porous Ceramics Thursday, June 6 10:30 a.m. 11:50 a.m. Garden Thursday, June 6 1:20 p.m. 3:20 p.m. Garden S5: ADVANCED POWDER PROCESSING AND MANUFACTURING TECHNOLOGIES Wednesday, June 5 8:30 a.m. 10:20 a.m. Stuart Wednesday, June 5 10:20 a.m. 11:50 a.m. Stuart Thursday, June 6 8:30 a.m. 10:20 a.m. Stuart Thursday, June 6 10:20 a.m. 11:10 a.m. Stuart Grinding and Dispersion Control Nano/Microstructure Control by Powder Processing II Thursday, June 6 11:10 a.m. 11:50 a.m. Stuart Thursday, June 6 1:20 p.m. 3:40 p.m. Stuart Nanoparticle and Powder Design and Synthesis Low-Cost and Energy-Saving Processing of Advanced Ceramics Advanced Powder Processing for Non-oxides Ceramics Thursday, June 6 3:40 p.m. 6:00 p.m. Stuart Friday, June 7 8:30 a.m. 10:20 a.m. Stuart Friday, June 7 10:20 a.m. Noon Stuart S6: SYNTHESIS AND PROCESSING OF MATERIALS USING ELECTRIC FIELDS/CURRENTS: A SYMPOSIUM HONORING PROF. ZUHAIR MUNIR Fundamentals Investigations in Current Assisted Densification | Monday, June 3 1:20 p.m. 5:40 p.m. Hanover Fundamentals Investigations in Current Assisted Densification II Consolidation of Nanocrystalline Materials I Consolidation of Nanocrystalline Materials II Property Evaluation of Materials Processing Using Electric Currents | Tuesday, June 4 8:30 a.m. 10:30 a.m. Hanover Tuesday, June 4 10:30 a.m. 11:50 a.m. Hanover Tuesday, June 4 1:20 p.m. 3:40 p.m. Hanover Property Evaluation of Materials Processing Using Electric Currents II Tuesday, June 4 Wednesday, June 5 3:40 p.m. 6:00 p.m. Hanover 8:30 a.m. 11:50 a.m. Hanover Synthesis, Functionalization, and Assembly of Metal Oxide Nanomaterials S8: ENGINEERING CERAMICS AND CERAMIC-MATRIX COMPOSITES: DESIGN, DEVELOPMENT, AND Properties and Characterization I 8:30 a.m. 10:30 a.m. 10:30 a.m. Noon 1:20 p.m. 4:50 p.m. 8:30 a.m. 10:40 a.m. S7: MULTIFUNCTIONAL METAL OXIDE NANOSTRUCTURES AND HETEROARCHITECTURES FOR ENERGY AND DEVICE APPLICATIONS Nanomaterials for Photocatalysis, Solar Hydrogen, and Thermoelectrics Integration of Functional Metal Oxide Nanostructures in Sensors and Devices Nanostructured Metal Oxides in Excitonic Solar Cells Thursday, June 6 Thursday, June 6 Thursday, June 6 Friday, June 7 Crown Crown Crown Crown Properties and Characterization II Ultra-High-Temperature Ceramics and Composites Applications in Aeronautics, Space, Automotive, Microelectronics, Energy, and Environmental Systems Wednesday June 5 Joining and Environmental Effects Thursday, June 6 Monday, June 3 Tuesday, June 4 Tuesday, June 4 APPLICATIONS 1:20 p.m. 6:10 p.m. 8:30 a.m. Noon 1:20 p.m. 5:40 p.m. Windsor Complex Windsor Complex Windsor Complex 8:30 a.m. Noon 8:30 a.m. Windsor Complex 11:40 a.m. Windsor Complex S9: MATERIALS FOR EXTREME ENVIRONMENTS: ULTRA-HIGH-TEMPERATURE CERAMICS (UHTCS) AND NANOLAMINATED TERNARY CARBIDES AND NITRIDES (MAX PHASES) Design of New Materials with Fascinating Properties New Methods for Joining and Testing Physical, Mechanical Properties and Oxidation Behavior Thursday, June 6 Thursday, June 6 Friday, June 7 1:20 p.m. 3:30 p.m. 3:30 p.m. 5:50 p.m. 8:30 a.m. 11:00 a.m. Windsor Complex Windsor Complex Windsor Complex American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 49 A World of Science www.ceramics.org/pacrim10 June 2-7, 2013 | Hotel Del Coronado | San Diego, Calif., USA The 10th Pacific Rim Conference on PACRIMO Ceramic and Glass Technology and Technology Including GOMD 2013 - Glass & Optical Materials Division Annual Meeting Sessions Date Time Location S10: ADVANCED CERAMIC COATINGS: PROCESSING, PROPERTIES, AND APPLICATIONS Advanced Thermal and Environmental Barrier Coatings | Thursday, June 6 8:30 a.m. Noon Tudor Advanced Thermal and Environmental Barrier Coatings II Thursday, June 6 1:20 p.m. 3:20 p.m. Tudor Multifunctional Coatings, Processing, and Advanced Surface Characterization Thursday, June 6 3:20 p.m. 5:50 p.m. Tudor Tribological, Wear- and Erosion-Resistant Coatings Friday, June 7 8:30 a.m. 10:20 a.m. Tudor Advanced Hybrid Coatings and New Processing Methods Friday, June 7 10:20 a.m. 11:50 a.m. Tudor S11: GEOPOLYMERS: LOW-ENERGY, ENVIRONMENTALLY FRIENDLY, INORGANIC POLYMERIC CERAMICS Processing and Characterization Monday, June 3 Microstructure and Mechanical Properties Tuesday, June 4 1:20 p.m. 8:30 a.m. 5:00 p.m. Tudor 11:50 a.m. Tudor S12: ADVANCES IN ELECTROCERAMICS Fundamental and Processing of Electronic Ceramics and Oxide Thin Films Tuesday, June 4 8:30 a.m. 10:20 a.m. Crystal Ferroelectric Thin Films and MEMS devices Tuesday, June 4 10:20 a.m. Noon Crystal Advanced Processing Tuesday, June 4 1:20 p.m. 3:40 p.m. Crystal Fundamental and Multi-ferroic Materials and Their Applications Tuesday, June 4 3:40 p.m. 5:50 p.m. Crystal Nanomaterials and Composites Dielectric Materials and Applications | Piezoelectric Materials and Devices Dielectric Materials and Applications II Piezoelectric Materials (Lead-Free I) Optical Properties and Their Applications Electrical or Magnetic Devices Piezoelectric Materials (Lead-Free II) S13: MICROWAVE MATERIALS AND THEIR APPLICATIONS Effect of Structure and Microstructure on Microwave Characteristics Tunable Dielectrics for Microwave Electronics I Wednesday, June 5 8:30 a.m. 10:20 a.m. Crystal Wednesday, June 5 10:20 a.m. Noon Crystal Thursday, June 6 8:40 a.m. 10:20 a.m. Crystal Thursday, June 6 10:20 a.m. Noon Crystal Thursday, June 6 1:20 p.m. 3:40 p.m. Crystal Thursday, June 6 3:40 p.m.- 5:50 p.m. Crystal Friday, June 7 8:30 a.m. 10:40 a.m. Crystal Friday, June 7 10:40 a.m. 11:50 a.m. Crystal Monday, June 3 1:20 p.m. 4:40 p.m. Stuart Monday, June 3 4:40 p.m. 6:20 p.m. Stuart Tunable Dielectrics for Microwave Electronics II Tuesday, June 4 8:30 a.m. 9:50 a.m. Stuart Ceramic Materials and Technology for Microwave and Millimeter Wave Devices Tuesday, June 4 9:50 a.m. 12:10 p.m. Stuart Characterization, LTCC, and Other Issues Tuesday, June 4 1:20 p.m. 5:30 p.m. Stuart S14: OXIDE MATERIALS FOR NONVOLATILE MEMORY TECHNOLOGY AND APPLICATIONS Oxide Materials for Nonvolatile Memory I Tuesday, June 4 1:20 p.m. 3:40 p.m. Tudor Oxide Materials for Nonvolatile Memory II Tuesday, June 4 3:40 p.m. 6:00 p.m. Tudor Oxide Materials for Nonvolatile Memory III Wednesday, June 5 8:30 a.m. 10:20 a.m. Tudor Oxide Materials for Nonvolatile Memory IV Wednesday, June 5 10:20 a.m. Noon Tudor S15: SOLID OXIDE FUEL CELLS AND HYDROGEN TECHNOLOGY Electrolytes Electrodes Monday, June 3 Tuesday, June 4 1:20 p.m. 6:00 p.m. Stacks, Interconnects, Sealants, Hydrogen Production Tuesday, June 4 8:30 a.m. Noon 1:20 p.m. 6:00 p.m. Bayside/Strand Bayside/Strand Bayside/Strand S16: DIRECT THERMAL TO ELECTRICAL ENERGY CONVERSION MATERIALS AND APPLICATIONS Oxide Thermoelectric Materials Monday, June 3 1:20 p.m. 3:40 p.m. Coastal High-Performance Bulk Thermoelectric Materials | Monday, June 3 3:40 p.m. 6:00 p.m. Coastal High-Performance Bulk Thermoelectric Materials II Tuesday, June 4 8:30 a.m. 10:20 a.m. Coastal Thermoelectric Materials: Skutterudites Tuesday, June 4 10:20 a.m. Noon Coastal Nanoscale and Thin-Film Thermoelectric Materials | Tuesday, June 4 1:20 p.m. 3:40 p.m. Coastal Thermoelectric Materials: Devices, Testing, and Materials Tuesday, June 4 3:40 p.m. 6:00 p.m. Coastal Thermoelectric Materials: Theory, Testing, and New Materials Wednesday, June 5 8:30 a.m. 10:20 a.m. Coastal Various Aspects of Thermoelectric Materials Research Wednesday, June 5 10:20 a.m. 12:10 p.m. Coastal Nanoscale and Thin-Film Thermoelectric Materials II Oxide Thermoelectric Materials and Theory Thursday, June 6 Thursday, June 6 8:30 a.m. 10:20 a.m. Coastal 10:20 a.m. Noon Coastal S17: PHOTOVOLTAIC MATERIALS AND TECHNOLOGIES Sensitized Solar Cell Materials and Systems I Thursday, June 6 1:20 p.m. 3:40 p.m. Coastal Sensitized Solar Cell Materials and Systems II Thin Films for Solar Energy Applications Materials Design and Characterization for Photovoltaic Applications 50 Friday, June 7 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 Thursday, June 6 3:40 p.m. - 6:00 p.m. Coastal Friday, June 7 8:30 a.m. 10:20 a.m. 10:20 a.m. Noon Coastal Coastal Sessions Date Time Location S18: CERAMICS FOR NEXT-GENERATION NUCLEAR ENERGY Silicon Carbide Technology for Nuclear Energy Wednesday, June 5 8:30 a.m. 10:20 a.m. Pacifica/Tide Silicon Carbide Composites for Fuel Cladding Wednesday, June 5 10:20 a.m. 11:50 a.m. Pacifica/Tide Material Design and Characterization Thursday, June 6 8:30 a.m. 10:20 a.m. Pacifica/Tide Materials and Fuels Synthesis Thursday, June 6 10:20 a.m. 11:40 a.m. Pacifica/Tide S19: ADVANCES IN PHOTOCATALYTIC MATERIALS FOR ENERGY AND ENVIRONMENTAL APPLICATIONS Photocatalytic Materials for Energy and Environment I Photocatalytic Materials for Energy and Environment II Photocatalytic Materials for Energy and Environment III Monday, June 3 Tuesday, June 4 Tuesday, June 4 1:20 p.m. 8:30 a.m. 6:00 p.m. Pacifica/Tide 11:50 a.m. Pacifica/Tide 1:20 p.m. 6:00 p.m. Pacifica/Tide S20: CERAMICS ENABLING ENVIRONMENTAL PROTECTION: CLEAN AIR AND WATER Ceramics Enabling Environmental Protection: Clean Air and Water Thursday, June 6 1:20 p.m. - 6:00 p.m. Pacifica/Tide S21: ADVANCED MATERIALS AND TECHNOLOGIES FOR ELECTROCHEMICAL ENERGY STORAGE SYSTEMS Electrochemical Energy Storage I Electrochemical Energy Storage II Electrochemical Energy Storage III Electrochemical Energy Storage IV Monday, June 3 Tuesday, June 4 Tuesday, June 4 Wednesday, June 5 1:20 p.m. 8:30 a.m. 6:00 p.m. Surf Noon Surf 1:20 p.m. 6:00 p.m. Surf 8:30 a.m. Noon Surf S22: GLASSES AND CERAMICS FOR NUCLEAR AND HAZARDOUS WASTE TREATMENT Nuclear Waste Glass Corrosion Nuclear Waste Glass Chemistry and Vitrification Monday, June 3 Thursday, June 6 1:20 p.m. 6:00 p.m. Crystal 8:40 a.m. 11:40 a.m. Surf Development and Characterization of Matrices for Waste Treatment and Immobilization Thursday, June 6 1:20 p.m. -5:00 p.m. Surf S23: ADVANCES IN BIOMINERALIZED CERAMICS, BIOCERAMICS, AND BIOINSPIRED DESIGNS Mineralization Processes, Self-Assembly, and Organic/Inorganic Structures Thursday, June 6 8:30 a.m. Noon Bayside/Strand Bioinspired and Biomimetic Ceramics and Composites and New Materials Natural Ceramics and Composites Thursday, June 6 Friday, June 7 1:20 p.m. 5:30 p.m. Bayside/Strand 8:30 a.m. 12:20 p.m. Bayside/Strand S24: NANOSTRUCTURED BIOCERAMICS AND CERAMICS FOR BIOMEDICAL APPLICATIONS Nanostructured Bioceramics I Monday, June 3 1:20 p.m. Nanostructured Bioceramics II Tuesday, June 4 8:30 a.m. 6:00 p.m. Noon Pointe Pointe JOINT SESSIONS SYMPOSIUM 23 AND 24 Joint Session I Tuesday, June 4 1:20 p.m. Joint Session II Wednesday, June 5 8:00a.m. 6:00 p.m. Noon Pointe Bayside/Strand GOMD SYMPOSIUM A: GLASS SCIENCE Darshana and Arun Varshneya Frontiers of Glass Science Lecture Monday, June 3 1:00 p.m. 1:50 p.m. Seabreeze Glass Transition and Relaxation I Monday, June 3 2:00 p.m. 6:00 p.m. Seabreeze George W. Morey Award Lecture Tuesday, June 4 8:00 a.m. 8:50 a.m. Seabreeze Glass Transition and Relaxation II Tuesday, June 4 9:00 a.m. 10:50 a.m. Seabreeze Non-oxide Glasses | Tuesday, June 4 10:50 a.m. 11:50 a.m. Seabreeze Norbert J. Kreidl Award Lecture Tuesday, June 4 1:00 p.m. 1:50 p.m. Seabreeze Non-oxide Glasses II Tuesday, June 4 2:00 p.m. 6:00 p.m. Seabreeze Glass Structure & Properties - Novel Glass Formers Wednesday, June 5 8:40 a.m. 10:20 a.m. Seabreeze Glass Structure & Properties - NMR Studies Wednesday, June 5 10:20 a.m. Noon Seabreeze The Stookey Lecture of Discovery Award Thursday, June 6 8:00 a.m. 8:50 a.m. Seabreeze Glass Structure & Properties - Mechanical Properties Thursday, June 6 9:00 a.m. Noon Seabreeze Glass Structure Thursday, June 6 1:20 p.m. Theoretical & Numerical Modeling Friday, June 7 8:30 a.m. Glass Structure & Properties - Characterization Friday, June 7 8:40 a.m. 5:40 p.m. Noon 11:00 a.m. Seabreeze Seabreeze Pacifica/Tide GOMD SYMPOSIUM B: GLASS TECHNOLOGY AND CROSS-CUTTING TOPICS Glassmelting and Thermal Processing Thursday, June 6 9:00 a.m. 11:20 a.m. Sunset Glass and Ceramics for Novel Applications I Thursday, June 6 11:20 a.m. 12:10 p.m. Sunset Ultrafast Science of Glass, Ceramics, and Materials Thursday, June 6 1:20 p.m. 3:20 p.m. Sunset Surface Reactions and Corrosion Thursday, June 6 3:20 p.m. 6:00 p.m. Sunset Glass and Ceramics for Novel Applications II Friday, June 7 8:30 a.m. 10:20 a.m. Sunset Glass Strengthening (Chemical, Mechanical, and Thermal) Friday, June 7 10:20 a.m. Noon Sunset GOMD SYMPOSIUM C: GLASSES FOR OPTOELECTRONIC AND OPTICAL APPLICATIONS Glasses for Sensing Monday, June 3 2:00 p.m. 3:40 p.m. Sunset Photoinduced Glass Modifications Monday, June 3 3:40 p.m. 6:00 p.m. Sunset Glasses with Nanoparticles Tuesday, June 4 9:00 a.m. 10:20 a.m. Sunset Photoluminescent Materials I Tuesday, June 4 10:20 a.m. Noon Sunset Photoluminescent Materials II Tuesday, June 4 2:00 p.m. 3:40 p.m. Sunset Glass Surface Modifications and Films Tuesday, June 4 3:40 p.m. - 6:00 p.m. Sunset Novel Optical Fibers | Novel Optical Fibers II Wednesday, June Wednesday, June 5 8:30 a.m. 10:20 a.m. Sunset 10:20 a.m. Noon Sunset GOMD SYMPOSIUM D: JAMES C. PHILLIPS HONORARY SYMPOSIUM Topological Constraint Theory of Glass I Topological Constraint Theory of Glass II Exponential Complexity in Materials Science and Biology Superconductivity Semiconductors, Pseudopotentials, and Dielectric Theory I Semiconductors, Pseudopotentials, and Dielectric Theory II Intermediate Phase I Monday, June 3 Tuesday, June 4 2:00 p.m. 9:00 a.m. 5:50 p.m. Palm 11:50 a.m. Palm Tuesday, June 4 2:00 p.m. 5:50 p.m. Palm Wednesday, June 5 8:30 a.m. 10:20 a.m. Palm Wednesday, June 5 10:20 a.m. 11:50 a.m. Palm Thursday, June 6 Thursday, June 6 9:00 a.m. 11:50 a.m. Palm Intermediate Phase II American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org Friday, June 7 8:30 a.m. 1:00 p.m. 5:50 p.m. Noon Palm Palm 51 13th Biennial Worldwide Congress on Refractories Unitecr 2013 The Unified International Technical Conference on Refractories www.unitecr2013.org Hosted by: The American Ceramic Society www.ceramics.org September 10-13, 2013 | The Fairmont Empress and Victoria Conference Centre | Victoria, BC, Canada REGISTER NOW! Save $150 through August 5th The Unified International Technical Conference on Refractories is a The Unified International Technical Chat contributes to the progress and exchange of industrial knowledge and technologies concerning refractories. UNITECR\'13 is designed for manufacturers, scientists, engineers, and industry professionals interested in the science, producThe technical program covers: ⚫ Advanced Testing of Refractories Cochairs: Len Krietz, Plibrico Co., USA; Nigel Longshaw, Ceram Research Ltd., UK ⚫ Advanced Installation Techniques & Equipment Cochairs: Jim Stendera, Vesuvius, USA; Hirohide Okuno, Taiko Refractories Co., Japan • Monolithic Refractories Cochairs: Dale Zacherl, Almatis, USA; Goutam Bhattacharya, Kerneos, India ⚫ Iron & Steel Making Refractories . Cochairs: Mike Alexander, Riverside Refractories, USA; Patrick Tassot, Calderys, Germany ⚫ Raw Materials Developments & Global Raw Material Issues Cochairs: Shane Bower, Christy Minerals LLC, USA; Phil Edwards, Imerys, France ⚫ Refractories for Glass Cochairs: M.D. Patil, Corning Inc., USA; Adam Wisley, Kopp Glass, USA ⚫ Cement & Lime Refractories • Cochairs: Fielding Cloer, Spar Inc., USA; Swapan Das, Central Glass & Ceramic Research Institute, India ⚫ Modeling and Simulation of Refractories Cochairs: Bill Headrick, Morco, USA; Harald Harmuth, Montanuniversität Leoben, Austria • • tion, and application of refractory materials. Attendees are involved in materials development, formulation, production, and engineering of refractories for ferrous and nonferrous metals industries as well as the minerals-processing, glass, cement, and petrochemical industries. Sign up at www.unitecr2013.org today! ⚫ Petrochemical Cochairs: Don McIntyre, ANH Refractories Co., USA; Ken Moody, Refractory System Solutions, USA ⚫ Refractories for Waste to Energy Processing & Power Cochairs: Ben Markel, Resco Products, USA; Andy Wynn, Morgan Ceramics, China Energy Savings through Refractory Design Cochairs: James Hemrick, Oak Ridge National Laboratory, USA; Valeriy Martynenko, Ukrainian Research Institute of Refractories Non-oxide Refractory Systems Cochairs: Dave Derwin, Superior Graphite, USA; Marcus Vinicius Moraes Magliano, Saint-Gobain, Brazil Refractories for Chemical Processes Cochairs: James Bennett, National Energy Technology Laboratory, USA; Matthias Rath, Austria • Developments in Basic Refractories Cochairs: Dominick Colavito, Minteq International Inc., USA; Andrie Garbers-Craig, University of Pretoria, South Africa ⚫ Global Education in Refractories Cochairs: George Oprea, University of British Columbia, Canada; Yawei Li, Wuhan University of Science and Technology, China Refractories for Nonferrous Metallurgy Cochairs: Rick Volk, United Refractories Co., USA; Angela Rodrigues-Schroer, Minteq, USA ⚫ Safety, Environmental Issues, and Recycling Solutions for Refractories Cochairs: Jason Canon, The Christy Refractories Co., USA; 52 62 Leonardo Curimbaba Ferreira, US Electrofused Minerals/Electro Abrasives, USA/Brazil www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 SCHEDULE AND EVENTS Keynote Speaker Remco De Jong Vice President and General Manager, Refractory Minerals Division, IMERYS Title: Minerals to materials: The changing face of the global refractory industry De Jong joined IMERYS Refractory Minerals group in July 2012. He was formerly the CEO of Almatis Group. With Almatis and previously with Corus Steel and Hoogovens, he held various senior management positions in Asia, Europe and the USA. He was involved in the development of new products and markets and in the optimization of processes and supply chains with global customers in automotive and portable energy end markets. Plenary Speakers Tom Vert General Manager of Primary Manufacturing, ArcelorMittal Dofasco Title: How do steelmakers pick refractories-Logic, emotion, or dartboard? Vert is the general manager of primary manufacturing at ArcelorMittal Dofasco, which includes cokemaking, ironmaking, steelmaking, and material handling and logistics. He has held this position since 2010. He graduated from McMaster University in 1987 with a BE (Ceramics) and received his MBA in 1994, also from McMaster University. Vert joined ArcelorMittal Dofasco in 1989 and has moved through a number of positions in steelmaking in technology and operations. He has been chairperson for the Refractory Division of the Canadian and American Ceramic Societies. Vert has served as chairperson of the UNITECR Refractory International Executive Board and is a Distinguished Life Member of this group. Charles E. Semler President/Consultant, Semler Materials Services Title: Trends for the world\'s most important, but least known products Semler has worked in the refractories industry since 1971. His refractories career began with Harbison-Walker Refractories Co. and then he was a professor of Ceramic Engineering and director of the Refractories Research Center at The Ohio State University for 12 years. Since 1986, he has worked as an independent refractories consultant, serving many US and foreign companies, including travel to 97 countries. He serves on the advisory board for several refractories publications-Interceram and Refractories World Forum (Germany), Journal of Technical Association of Refractories, Japan, and China\'s Refractories. He has written more than 200 papers, delivered lectures and conducted workshops around the world, and holds four patents. Semler has received the following honors/awards: Fellow of The American Ceramic Society; Distinguished Life Member of UNITECR; T.J. Planje St. Louis Refractories Award; Service Award from Technical Association of Refractories, Japan (TARJ); elected to the International Academy of Ceramics; and Tredennick Award from The Refractories Institute (USA). American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 2013 Officers Louis J. Trostel Jr., President Rob Crolius, Treasurer Dana Goski, Technical Program Chair Nancy Bunt, Social Program Chair Short Courses Sponsored by ANH fiRe Tuesday, September 10, 2013 8 a.m. to 5 p.m. Early-Bird Rate: $595 | Regular Rate: $745 Dispersion and Packing of Ceramics Particles for Advanced Refractory Castables Instructors: Ana Paula Luz, Mariana A. Braulio, and Victor C. Pandolfelli, Federal University of São Carlos, Brazil Fundamentals on Corrosion Behavior of Refractories Instructors: Christos Aneziris, Technical University Freiberg, Germany, and Jacques Poirier, University of Orleans, France A limited number of student scholarships are available. Visit www.unitecr2013.org for details. Schedule at a Glance Tuesday, September 10, 2013 FIRE Corrosion Short Course FIRE Castable Short Course Welcome Reception at British Columbia Museum Wednesday, September 11, 2013 Opening Session and Keynote Speaker, Remco De Jong Exhibits Concurrent Technical Sessions Poster Session Thursday, September 12, 2013 Plenary Speaker, Tom Vert Concurrent Technical Sessions Exhibits Concurrent Technical Sessions Conference Dinner Friday, September 13, 2013 Plenary Speaker, Charles Semler Concurrent Technical Sessions Lunch and Closing Ceremony 8:00 a.m.-5:00 p.m. 8:00a.m.-5:00 p.m. 7:00-10:00 p.m. 8:40 10:00 a.m. 10:00 a.m.- 6:00 p.m. 10:40 a.m.-5:40 p.m. 5:30-7:00 p.m. 8:10 9:00 a.m. 9:20 a.m. 12:40 p.m. 9:30 a.m.-5:00 p.m. 2:20-6:10 p.m. 7:00-10:00 p.m. 8:00 9:00 a.m. 9:20 a.m. 12:40 p.m. 1:00-2:00 p.m. Breaks and lunches take place in the Exhibit Hall. 53 13th Biennial Worldwide Congress on Refractories Unitecr 2013 The Unified International Technical Conference on Refractories www.unitecr2013.org Hosted by: The American Ceramic Society www.ceramics.org September 10–13, 2013 | The Fairmont Empress and Victoria Conference Centre | Victoria, BC, Canada Sponsors ALMATIS kerneos PREMIUM ALUMINA IMERYS TRANSFORM TO PERFORM ▶CALUCEM C-E Minerals CHRISTY MINERALS Exhibits Companies who want to network and do business with refractory related manufacturers, users, technologists, and scientists should contact us today for premium exhibit space. For more information, contact Patricia Janeway at +1 614-794-5826. ALTEO Exhibitors BassTech International Booth Number 21 17 15 11 C-E Minerals Eirich, Maschinenfabrik Gustav Eirich GmbH & Co KG Elkem Fibercon International Inc. Huang He Minerals Co. Ltd. Jinan Shengquan Hepworth Resin Co. Ltd. Kerneos Laeis GmbH Orind Special Refractories Ltd. Putzmeister Shotcrete Technology Refmin China Co. Ltd. Riedhammer GmbH RÜTGERS Basic Aromatics GmbH Steuler-KCH GmbH VELCO GmbH Exhibit Hours: Wednesday, September 11, 2013 10:00 a.m. to 6:00 p.m. Thursday, September 12, 2013 9:30 a.m. to 5:00 p.m. Breaks and lunches will be in the exhibit hall. 19 29 18 9 242013262226TRI ALUMINATE TECHNOLOGIES THE REFRACTORIES INSTITUTE RefractoryCeramicsDivision Ceramic Society KROSAKI HARIMA KROSAKI HARIMA CORPORATION Optional tour NARCO Harbison ANH Refractories AP Green ALUCHEM inc Refined Minerals and Chemicals VIRGINIA K KYANITE кажем Take advantage of optional tours during UNITECR\'13, and experience afternoon tea at The Empress. Visit www.unitecr2013.org/tours to sign up. Victoria City Tour and Butchart Gardens Monday, September 9, 9:00 a.m. to 12:30 p.m. | $81 CAD Whale Watching Tuesday, September 10, 2:00 p.m. to 5:00 p.m. | $95 CAD Goldstream Park Excursion and Cowichan Valley Winery Wednesday, September 11, 10:00 a.m. to 4:00 p.m. | $96 CAD Afternoon Tea at The Empress 12:00 p.m. daily | $59.95 CAD, $50 CAD for hotel guests 54 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 The American Ceramic Society www.ceramics.org www.ceramics.org/iccps12 th August 4-7, 2013 Hilton Portland & Executive Towers Portland, Ore. 12\" International Conference on Ceramic Processing Science (ICCPS-12) ICCPS-12 has evolved from a focus on particle-based processes to now including thin-film processes, precursor approaches, and all facets of the science underlying the basic themes of control and tailoring of ceramic-based materials with specific microstructure-property goals. ICCPS-12 marks the 27th anniversary of the ceramic processing science series. Since 1986, the discipline has made significant progress in colloid and surface chemistry, powder synthesis, precursor-derived systems, and sintering. However, much needs to be done to advance the scientific underpinnings of these processes as well as the emergent areas of nanotechnology and its associated challenges, particle assembly, patterning, additive manufacturing, rapid sintering, and densification of complex shapes and multimaterial combinations. Register by June 28th to save $150. Schedule Sunday, August 4 Registration Monday, August 5 Registration Welcome & Plenary Concurrent Sessions Plenary Concurrent Sessions 3:00 p.m. - 6:00 p.m. 7:00 a.m. 7:00 p.m. 8:00 a.m. 9:00 a.m. 9:20 a.m. Noon 1:00 p.m. 1:40 p.m. 1:45 p.m. 5:20 p.m. Welcome Reception & Poster Session 1 5:00 p.m. - 7:30 p.m. Tuesday, August 6 Registration Plenary Concurrent Sessions Poster Session 2 Banquet Wednesday, August 7 Registration Plenary Concurrent Sessions Plenary Concurrent Sessions 7:30a.m. - · Noon 8:00 a.m. 8:40 a.m. 9:00 a.m. Noon 5:00 p.m. 7:00 p.m. 7:00 p.m. 9:30 p.m. 7:30 a.m. 4:00 p.m. 8:20 a.m. 9:00 a.m. 9:20 a.m. Noon 1:00 p.m. 1:40 p.m. 1:45 p.m. 4:30 p.m. Hilton Portland & Executive Towers 921 SW Sixth Ave. | Portland, OR 97204 | 503-226-1611 Rate: $169 Cut off Date: June 26, 2013 Plenary Speakers David Pine Professor of Physics and Mathematics and Director of the Center for Soft Matter Research, New York University, USA Title: Colloids with directional interaction Hiroaki Imai Professor, Keio University, Japan Title: Bioinspired techniques, and mesoscale and microscale hierarchical assembly Christophe Martin Grenoble INP, France Title: Simulations of particle-packing effects on sintering defects and deformation Ludwig Gauckler Professor, ETH, Switzerland Title: Innovations through processing of ceramics and ceramic composites James J. Watkins Director of Center for Hierarchical Manufacturing, University of Massachusetts, USA Title: Roll-to-roll processing of functional materials and devices Technical Program ICCPS-12 includes plenary sessions in the morning and afternoon as well as concurrent sessions with invited and contributed presentations. Two poster sessions also are planned. The technical program covers • Particle shape control and assembly • Colloid dispersion and surface modification Rheology of concentrated suspensions • Microfluidic techniques • Patterning, templates, and self assembly • Wet- and dry-shaping methods, including additive manufacturing • Solution and precursor thin-film processes • Biomimetic and bioinspired techniques • Computational tools applied to processing • Novel characterization and imaging tools • Densification (nanoscale, multimaterial, complex shapes, novel approaches) • Mesoscale, microscale, and hierarchical manufacturing and design of microstructure • Processes and processing designed to advance specific energy, electronic, optical, and structural applications American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 55 REGISTER NOW! 4th Advances in Cement-Based Materials: Characterization, Processing, Modeling, and Sensing July 8-10, 2013 | University of Illinois at Urbana-Champaign | Urbana, III. Cements 2013 is coorganized by the Cements Division of ACerS and the Center for Advanced Cement-Based Materials. By colocating with ACBM, the Cements Division will build upon our core audience, offer strong student activities for training, and bring in new members. DELLA ROY LECTURE Leslie J. Struble Department of Civil Engineering, University of Illinois Calcium in geopolymers Struble has been a University of Illinois faculty member since 1989. She conducts research and consulting activities involving various aspects of concrete performance. She has authored or coauthored more than 140 cement and concrete publications. PROGRAM COCHAIRS Paramita Mondal Assistant Professor, University of Illinois, pmondal@illinois.edu David Lange Professor, University of Illinois, dlange@illinois.edu Tyler Ley Associate Professor, Oklahoma State University, tyler.ley@okstate.edu CEMENTS DIVISION LEADERSHIP Division Chair: Benjamin Mohr, Tennessee Technological University Chair-Elect: Kyle Riding, Kansas State University Secretary: Jeff Chen, Lafarge Ceutre de Recherche Trustee: Joseph J. Biernacki, Tennessee Technological University 56 SYMPOSIA • Cement chemistry and nano/microstructure Hydration of cement, aqueous thermodynamics and high-temperature chemistry, supplementary cementitious materials, structure and properties of C-S-H and C-S-H composites, and microstructure evolution. • Advances in material characterization techniques New developments regarding experimental techniques for characterizing hydration, nano/microstructure, early age properties, rheology, hardened properties, durability, and other physical and chemical phenomena of cementitious materials and cement-based composites. Alternative cementitious materials Manufacture of next-generation cements, including low energy/\"green\" cements, geopolymers, and other novel binders. Addition of nanosized and nanostructured materials, including organic additives and their interactions in cementitious systems. • Durability and lifecycle modeling Properties of cement pastes governing durability, concrete deterioration mechanisms, methodology for testing durability, transport processes, and service life predictions. • Advances in computational material science and chemomechanical modeling of cement-based materials New developments in modeling the behavior of cement-based materials, including chemical, mechanical, and physical behavior as applied to durability and interaction of cementitious materials with the environment; hydration kinetics; and microstructural evolution modeling. • Smart materials and sensors Advances in sensor technology for monitoring fresh, hardened properties as well as physical and chemical degradation processes. Rheology and advances in SCC New development in measuring behavior of fresh concrete, modeling viscosity and yield stress, methods, and application of self-consolidating concrete. HOTEL Illini Union 1401 W. Green St., MC-384, Urbana, IL 61801 Reserve your room online or at 217-333-1241. Mention ACerS Conference to secure the conference rate. Rates: Double $99, plus tax Queen $104, plus tax King $109, plus tax Cutoff Date: June 8, 2013 Hampton Inn 1200 W. University Ave., Urbana, IL 61801 Reserve your room online or at 217-333-1100. Mention ACerS Conference to secure the conference rate. Rates: Double $119, plus tax King $119, plus tax Cutoff Date: June 8, 2013 The American Ceramic Society www.ceramics.org www.ceramics.org/cements2013 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 H Refractory Ceramics Division Record attendance at St. Louis Section/RCD 49th Annual Symposium on Refractories The American Ceramic Society 201 (Credit for all photos: ACerS.) 1 The Planjes previous Planje Award winners with 2013 winner, J.P. Willi. 2 The RCD leadership. From left: Lora Cooper Rothen, ACerS RCD board liaison; Lou Trostel, counselor; Bill Headrick, immediate past chair, Dave Tucker, chair; Jens Decker, secretary; Ben Markel, vice chair; and Josh Pelletier, member-at-large. 3 Conner Jackson with his grandfather, J.P. Willi. Jackson found the shades\'stache combo on a trip to Willi\'s hometown of Chicago. Is there a refractories career in Jackson\'s future? 4 Paul Schlett of Valero Energy Corp. introduces the first speaker, Ed Linck of Linck Refractory Services. Together they have more than 100 years experience meeting the refractory needs of the refining industry. 5 Vendors met attendees at the expo and networking reception. 6 Wagner Silva of Magnesita Refractories presents the work that was the basis of his Allen Award-winning JACerS paper. 7 ACerS president, Richard Brow, reports on ACerS activities and new initiatives to promote ceramic engineering education. 6 A 5 tons of refractory material to line a FCCU, the refinery sector accounts for only 5-10 percent of the overall refractories market. Parkinson says there are about 500 FCCUs worldwide that account for about 40 percent of the global gasoline production. A FCCU can process 20,000–200,000 barrels of oil per day. The catalytic cracking reaction occurs at 500-550°C, and the catalysts are primarily zeolite and aluminosilicate fine powders. John Hellmann, from Pennsylvania State University, is working on proppant technology, the vortex of current events relating to hydrofracturing. He says that the Marcellus Shale reserve has natural gas reserves to record-breaking 200 attended the 49th supply the US energy needs for 150 years, which he Annual Symposium on Refractories. The theme of the symposium at this year\'s St. Louis Section/Refractory Ceramics Division meeting was \"Refractory Challenges in the Chemical and Petro-Chemical Industries.\" Ed Linck provided an overview of refractories challenges and technologies in the refining industry, particularly as they are used in fluid catalytic cracking units (FCCUs). In the 1950\'s, FCCUS ran 6-9 months before needing repair. Today, FCCUS run five years continuously, and new technologies are driving the life cycle toward seven years. Linck noted that good materials are important, but installation is critical. \"You can have the best material in the world, but if you don\'t put it in right, it won\'t work right,\" he says. Downtime costs a refiner about $1 million per day, according to Richard Parkinson of UOP LLC/Honeywell. Even though it takes 100–150 American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org describes as \"the Saudi Arabia of natural gas.\" \"This is an industry that is going to be large,\" Hellmann says, \"and we have to do it right.” An important part of \"doing it right\" is advancing the proppant technology. Each lateral well (12-20 come off each vertical wellhead) calls for 3,000 tons of proppant. The present market is in the neighborhood of 100 billion tons per year, up from 12 billion tons seven years ago. Proppants need to be available locally and cheap. His group is looking at ways to use discarded materials-glass cullet, slags, wrong-size roofing shingle minerals, and drill cuttings pulled from the wells-to make highquality, inexpensive proppants, while solving industrial disposal problems. He also offered some intriguing ideas for \"smart proppants\" based on magnetic particles with piezoelectric outer shells that could provide in situ monitoring of the wells. Other talks in the two day symposium addressed chronically challenging issues such as corrosion, heat, and abrasion. 57 book review Review of The Wright writes that Bragg was ambivalent about covalent bonding to explain the Constitution of Glass tetrahedral coordination of silicon by The Society of Glass Technology (SGT) recently published its first volume of Historical Papers in Glass Science & Technology under the title The First Symposium on the Constitution of Glass (Society of Glass Technology, Sheffield, England, 2012). This volume contains facsimile copies of eight papers and discussion notes from a 1925 symposium of the same title organized by W.E.S. Turner. It also contains two related papers and updated notes published by the SGT in 1927. The editor of this new volume, Adrian C. Wright (professor emeritus, University of Reading, United Kingdom), added two significant papers on diffraction studies of glass structure, published by the SGT in 1930, and a translation of an important paper by Lebedev, from 1921. This collection of papers provides a fascinating snapshot of the state of glass science immediately before the publication of Zachariasen\'s seminal paper, \"The atomic arrangement in glass,\" in 1932.¹ What makes this volume compelling for anyone interested in the historical roots of modern glass science, however, are the introductory notes prepared by Wright. The notes succinctly summarize each original paper and provide an historical context about the contemporaneous understanding of the nature and constitution of glasses. Wright describes how that understanding evolved, particularly as structural information from rapidly improving X-ray diffraction techniques emerged. Scientists like W.H. Bragg (whose study of the structures of α- and ẞ-quartz is in this collection) were challenging the notion that crystalline solid structures were arrangements of stoichiometric molecules. He and others proposed instead structures based on atomic arrangements, such as the \"chessboard pattern\" of Na* and Cl- ions in NaCl. Such ideas, however, were not yet fully formed nor extended to crystalline (or amorphous) networks. For example, 58 oxygen in quartz and the presence of corner-sharing tetrahedral. This suggests that Bragg viewed the structures in terms of oxygen packing, not Si-O bonding. The glass scientists of the time clearly were attempting to relate the structures of crystalline solids to those of glass. The consensus was that glass structure was heterogeneous, at least at the nanoscale, with molecular clusters or crystallites The First Symposium on THE CONSTITUTION OF GLASS with reduction and Commentary by Adrian C. WRIGHT comprising the overall glass structure. Such ideas are perhaps most explicit in Lebedev\'s paper. He ascribes reversible changes in the thermal properties of silicate glasses around 550°C-600°C to the aß transformation of quartz crystallites. Subsequent diffraction studies, including those of Randall, Rooksby, and Cooper (reproduced in this volume) predicted crystallite sizes on the order of 1-10 nm. In retrospect, Lebedev was recording evidence of the glass transition, not an underlying crystallographic transformation. Several other papers in the collection also describe the \"endothermic transition.\" A paper by Tool and Hill describes the effects of thermal history on the density and refractive index of several glasses. Here, we see evidence for relaxation phenomena that eventually are explained by Tool\'s fictive temperature concept² and Narayanaswamy\'s analytical methods.³ Likewise, Tamman\'s paper, \"Glasses as supercooled liquids,\" provides much of the foundation for the Richard K. Brow Guest columnist kinetic theory of glass formation, developed by Uhlmann and others decades later. One of the most interesting papers in the collection is Rosenhain\'s, \"The structure and constitution of glass.\" Rosenhain assumed that the structures of crystals and glasses could be understood as assemblages of atoms linked by bonds and that interatomic forces would determine equilibrium bond lengths and bond angles. Rosenhain postulates that the atoms in crystalline materials form regular, \"strain-free” arrangements. As Wright notes, Rosenhain anticipates many of the important concepts of Zachariasen\'s work and what eventually became known as the continuous random network model of glass structure. Rosenhain says in his paper, \"On the experimental side as well as on the theoretical, glass has proved singularly elusive.\" Almost 70 years later, Anderson, 5 more or less, said the same thing when he famously stated that, “The deepest and most interesting unsolved problem in solid-state theory is probably the nature of glass and the glass transition.\" This is not to say that we have not advanced our understanding of the constitution of glass since Turner organized this symposium in 1925. Rather, like our predecessors realized almost 90 years ago, the more deeply we study glasses, the more we realize that we do not yet quite understand them. To order, visit www.orders.sgthome. co.uk/gbuO-prodshow/constitutionofglass.html. About the author Richard K. Brow is Curator\'s Professor of Ceramic Engineering, Materials Science and Engineering Department, Missouri University of Science and Technology, Rolla, Mo. References \'W.H. Zachariasen, \"The atomic arrangement in glass,\" J. Am. Chem. Soc., 54, 3841 (1932). ZA.Q. Tool, \"Relation between inelastic deformability and thermal expansion of glass in its annealing range,\" J. Am. Ceram. Soc., 29 [9] 240-53 (1946). 3O.S. Narayanaswamy, \"A model of structural relaxation in glass,” J. Am. Ceram. Soc., 54 [10] 491-98 (1971). *D.R. Uhlmann, \"A kinetic treatment of glass formation,\" J. NonCryst. Solids, 7, 337-48 (1972). 5P.W. Anderson, \"Through the glass lightly,\" Science, 267, 1615 (1995). www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 ●resources Calendar of events May 2013 7-8 Glassman Europe 2013 - Expo XXI, Warsaw, Poland; www.glassmanevents.com/europe 13-15 Structural Clay Products Division Meeting (in conjunction with The National Brick Research Center) - Salt Lake City, Utah; www.bit.ly/12FYITO 20-24 PPXRD-12: 12th Pharmaceutical Powder X-ray Diffraction Symposium – Institute of Physics, Chinese Academy of Sciences, Beijing, China; www.icdd. com/ppxrd 21 United States Advanced Ceramics Association Technical Meeting 2013 - National Academy of Public Administration, Washington, D.C.; www. advancedceramics.org 23 Glass Focus Conference - Radisson Blu Hotel, Manchester Airport, Manchester, UK; www.britglass.org.uk/ Glass-Focus-2013 24-27 China Glass 2013 - China Int\'l Exhibition Center, Beijing, China; www. bit.ly/11Rev3h 28-June 1 Ceramics China 2013: China Int\'l Exhibition for Ceramics Technology, Equipment, and Product Pazhou Complex, Guangzhou, China; www.ceramicschina.com.cn June 2013 1-7 Sintering Short Course (organized by ACerS and held in conjunction with PACRIM 10, see below); www.bit.ly/ VvyzMX 2-7 PACRIM 10: The 10th Pacific Rim Conference on Ceramic and Glass Technology, including the Glass & Optical Materials Division Annual Meeting - Hotel Del Coronado, San Diego, Calif.; www.ceramics.org/pacrim10 4-5 Materials 2013 Trade Fair and Conference - NH Conference Centre Koningshof, Veldhoven, Netherlands; www.materialenbeurs.nl 5-6 Fundamentals of Glass Science and Technology Short Course (organized by ACers and held in conjunction with PACRIM 10, see above); www.bit. ly/XimnBK 7-12 NCM12: 12th Int\'l Conference on the Structure of Non-Crytalline Materials - Riva del Garda, Trento, Italy; http:// events.unitn.it/en/ncm12 17-20 Mir Stekla/World of Glass Int\'l Exhibition - Expocentre Fairgrounds, Moscow, Russia; www.mirstekla-expo.ru 19-20 2013 ACerS-NSF Ceramic Materials Principal Investigator Workshop - NSF Headquarters, Arlington, Va.; www.bit.ly/Y3Dfsg 19-22 ECers Summer School: Ceramic Science and Technology for the 21st Century - Ester Technopole, Limoges, France; www.ecers2013.fr 23-27 Summer School of Calorimetry 2013: \"Calorimetry and Thermal Methods in Catalysis\" - CNRS, Fourvière Hill, Lyon, France; http://calo.catalyse.cnrs.fr 23-27 ECers XII: 13th Conference of the European Ceramic Society - Ester Technopole, Limoges, France; www. ecers2013.fr 26 Porous Ceramics for Concentrating Solar Power Applications - Lugano, Switzerland; www.supsi.ch/go/ CMC4CSP July 2013 1-5 Int\'l Commission on Glass XXIII Int\'l Congress - Prague, Czech Republic; www.icglass.org 8-10 ACers Cements Division Annual Meeting - University of Illinois at Urbana-Champaign, Champaign, III.; www.bit.ly/TwvbRd 8-11 ➡ MC11: 11th Int\'l Conference on Materials Chemistry - University of Warwick, Warwick, UK; www.rsc.org/ mc11 8-12 ICG Summer School: 5th Workshop for New Researchers in Glass Science and Technology - University of Montpellier, Montpellier, France; www. bit.ly/ZrJSU1 10-12 CERMODEL2013: Modeling and Simulation Meet Innovation in Ceramics Technology - Trento, Italy; http://events.unitn.it/en/cermodel2013 11-12 SOFC-PPP: Solid Oxide Fuel Cell Promise, Progress, and Priorities - Westin Arlington Gateway Hotel, Alexandria, Va.; www.sofcwg.org 28-Aug. 1 MCARE 2013: Materials Challenges in Alternative and Renewable Energy 2013 - Silk Road Dunhuang Hotel, Dunhauang, Gansu, China; http:// mcare2013-dunhuang.dconference.cn August 2013 4-7 ICCPS-12: Int\'l Conference on Ceramic Processing Science - Hilton Portland & Executive Tower Portland, Portland, Ore.; www.bit.ly/Wn7mNJ 25-28 MMM2013: 15th IFAC Symposium on Control, Optimization, and Automation in Mining, Mineral, and Metal Processing - Hyatt Regency Mission Bay Spa & Marina, San Diego, Calif.; www.flogen.org/mmm2013 September 2013 2-5 DCM 2013: Int\'l Conference on Diamond and Carbon Materials - Riva del Garda, Italy; www.diamond-conference.elsevier.com 11-12 GlassBuild America 2013Georgia World Congress Center, Atlanta, Ga.; www.glassbuildamerica.com 10-13 UNITECR 2013 - The Fairmont Empress and Victoria Conference Centre, Victoria, British Columbia, Canada; www. unitecr2013.org 22-26 ➡ HTCMC-8: 8th Int\'l Conference on High-Temperature Ceramic-Matrix Composites - Qujiang Int\'l Exhibition Center, Xi\'an, China; www.htcmc8.org 25-27 Int\'l Ceramic Exhibition - Tokyo Big Sight East Hall, Tokyo, Japan; www. ceramic-expo.jp 29-Oct. 2 Fractography of Advanced Ceramics - Smolenice Castle, Smolenice, Slovakia; www.imr.saske.sk Dates in RED denote new entry in this issue. Entries in BLUE denote ACerS events. denotes meetings that ACerS cosponsors, endorses or otherwise cooperates in organizing. American Ceramic Society Bulletin, Vol. 92, No. 4 | www.ceramics.org 59 classified advertising Career Opportunities ACers is Hiring... ASSOCIATE EDITOR Bulletin and Ceramic Tech Today Are you an experienced editor or science writer with a degree in materials science, engineering, or the physical sciences? The American Ceramic Society is hiring an Associate Editor to report, write and develop print, video and online content, and assume some production management responsibilities. Experience with web-based publishing systems and prepress publishing processes are desirable. This full-time position is located in the ACerS headquarters office in Columbus (Westerville) Ohio, and offers competitive compensation plus strong growth potential. Information on the position requirements and application process can be found on the ACerS Career Center at careers.ceramics.org. 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Place Your Ad in the Bulletin\'s Classified 62 62 www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 ORDER VERSION 3.4 The Society ACERS-NIST www.ceramics.org/phasecd PHASE EQUILIBRIA DIAGRAMS FOR CERAMIC SYSTEMS Download the Version 3.4 demo for free! www.ceramics NIST National Institute of Standards and Technology US Department of Commerce AMERICAN CERAMIC SOCIETY Obulletin Advertiser ACCCO Inc./Burley Clay Products 800-828-7539 remmert@accco-in.com www.accco-inc.com MAY 2013 ADVERTISER INDEX Page No. Advertiser Page No. 61 Mohr Corp. 62 810-225-9494 sales@mohrcorp.com • www.mohrcorp.com AdValue Technology 502-514-1100 sales@advaluetech.com 60 Netzsch Instruments NA, LLC 62 781-272-5353 www.advaluetech.com nib-sales@netzsch.com • www.netzsch.com American Ceramic Society, The Inside front cover, Powder Processing & Technology 61 www.ceramics.org 29, 35, 39, 60, Inside back cover American Elements Outside back cover www.americanelements.com Carbolite Inc. 15 info@prematechac.com 800-543-6208 sales@carbolite-usa.com • www.carbolite.us 219-462-4141 x224 asukovich@pptechnology.com www.pptechnology.com 508-791-9549 Quality Executive Search Inc. 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Cleveland Ave, Suite 210 Ceramic The American Society www.ceramics.org 63 O deciphering the discipline Computational simulation of structure and diffusion in bioactive glass Disease, aging, and accidents require treatment or replacement of some human organs. When possible, autograft harvesting of healthy tissue from one site of a patient treats the dysfunctional part elsewhere. The need for two surgeries increase the patient\'s pain, blood loss, and recovery time. Sometimes, healthy people donate tissue, but potential problems exist, such as availability of a donor, organ compatibility, and the chance of disease transfer. Synthetic biomaterials may provide mechanical, biological, and physiochemical advantages when used as grafts. 1 Conventional bioactive glasses were introduced by Larry Hench and co-workers. They were based on sodium calcium phosphosilicate glasses. Since then, the field of bioceramics has expanded to include many new compositions. Yet, the first and best-studied composition is 45S5 Bioglass (45% SiO2, 24.5% Na₂O, 24.5% CaO, and 6% P₂O, by weight percent). It still is considered to be one of the most bioactive compositions. In our work, we tailor glass compositions by introducing elements with beneficial effects, such as anti-inflammatory factors and bone-growth enhancements. The element strontium, for example, has a beneficial effect on bone growth. In bone metabolism, there is competi tion between bone growth and bone absorption. Strontium has dual effects. It can boost the activity of osteoblast cells that control bone growth. On the other hand, it can inhibit osteoclast cells, which regulate bone desorption.² Thus, strontium-containing bioglasses are promising new bioactive glass compositions with enhanced bioactivity and tissue regeneration capabilities for bone and tooth repair and in biomedical applications, such as tissue engineering. Computational simulation methods 64 44 have emerged as important complements to experimental materials research. Classical molecular dynamics (MD) simulations apply Newton\'s second law to determine the movement of atoms in response to appropriate force fields or interatomic interactions. MD can provide atomic-level structural detail for glass and other amorphous materials at local and intermediate length scales. Bioactive materials implant surfaces undergo a time-dependent, kinetic modification on implantation. Therefore, dynamic information also is important for understanding bioactivity. MD simulations can provide valuable information for studying dynamic properties and ionic diffusion properties. Because of the chemical similarity of strontium and calcium, substituting Sro for CaO in 45S5 effectively develops novel bioglass compositions. We investigated the structure and dynamic properties of 45S5 as a function of SrO/CaO substitution using MD simulations. Locally, strontium ions have an average coordination number of 7.0 and bond length of about 2.59 Å. The SrO/ CaO substitution does not affect the firstneighbor environment of network formers (silicon and phosphorus), while other network modifiers show a slight decrease in average coordination number. The medium-range glass structure was characterized with Q distribution (where n is the number of bridging oxygen in the SiO or PO tetrahedron, Q) and was independent of the degree of SrO/CaO substitution. Also, we found the cooling rate used for simulating the melting-and-quenching process changed the Q distribution, especially for phosphorus.³ Such findings shed light on the investigation of intermediate-range structural features when applying MD simulations. In terms of a diffusion energy barrier, the diffusion behavior of modifiers is not influenced by SrO/ CaO substitution, although the addition of strontium into 4585 does influence the dynamic behavior of calcium and sodium in the melt, as illustrated from Ye Xiang Guest columnist MD simulation of SiO and PO tetrahedra network highlighting the coordination environment of calcium, sodium, and strontium. Color legend: yellow is silicon; red is oxygen; light purple is phosphorus; blue is sodium; purple calcium; and green is strontium. velocity auto correlation functions. Besides, the features of the total vibrational spectra remain unchanged with SrO/CaO substitution. Therefore, the experimentally observed higher dissolution rate of strontium-containing glass can be explained with the increased free volume and weakened chemical bonds in the Si-O network, rather than being the result of change in alkali/alkali-earth diffusion rates.4 Ye Xiang is a graduate student in the Department of Materials Science and Engineering, University of North Texas, Denton, Tex. She completed her undergraduate work in material science and engineering at Wuhan University of Technology, Wuhan, China. Her PhD advisor is Jincheng Du, associate professor at UNT. References \'W. Cao and L.L. Hench, \"Bioactive materials,\" Ceram. Int., 22, 493-507 (1996). 2R.G. Hill, A. Stamboulis, R.V. Law, A. Clifford, M.R. Towler, and C. Crowley, \"The influence of strontium substitution in fluorapatite glasses and glass-ceramics,\" J. Non Cryst. Solids, 336, 22329 (2004). 3Y. Xiang and J. Du, “Effect of strontium substitution on the structure of 45S5 Bioglasses,\" Chem. Mater., 23, 2703-17 (2011). J. Du and Y. Xiang, “Effect of strontium substitution on the structure, ionic diffusion, and dynamic properties of 45S5 bioactive glasses,\" J. Non Cryst. Solids, 358, 1059-71 (2012). ■ www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 4 (Credit: Xiang; UNT) www Call for Papers Abstracts Due July 17, 2013 38TH INTERNATIONAL CONFERENCE AND EXPOSITION ON ADVANCED CERAMICS AND COMPOSITES January 26-31, 2014 Hilton Daytona Beach Resort and Ocean Center Daytona Beach, Florida, USA www.ceramics.org/icacc2014 102 02010N 102 304 05 06 07 08 NE The American Ceramic Society www.ceramics.org Organized by The American Ceramic Society and ACerS Engineering Ceramics Division Engineering Ceramics Division HIA-co Cene Sex d\'y strontium doped lanthanum III-IV nitride materials es org H metallics tantalum alloys cerium polishing powder dysprosium pellets atomic layer deposition solid Li Be ite Na Mg misch aerospace ultra-light alloys scandium-aluminum green technology crystal growth cobalt metamateria thin film bid Henetics rod B C N F Ne iridium crucibles erbi Al Si P S CI Ar ultra hacro K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr cathol van solare Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I CIGS superd Xe lucke Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn battery lithium super alloys yttrium foil Surface functionalized nanoparticles palladium shot anode Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu cone! nand tantalu gallium lump iTh Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr nano gels gallium arsenide carbon nanotubes titanium robotic parts spintronics laser crystals rare earth metals fuel cell materials rgets silicon carbide dielectrics 田 um gold nanoparticles hafnium tubing eun TM LED lighting iron Now Invent. germanium windows AMERICAN ELEMENTS platinum ink 99.999% ruthenium spheres erbium doped fiber optic quantum dots anti-ballistic ceramics World\'s Leading Manufacturer of Engineered & Advanced Materials shape memory alloys rhodium sponge nickel foam ultra high purity m osmium Nd:YAG alternative energy ioni catalog: americanelements.com photovoltaics ©2001-2011. 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