Glimpsing glass structure under pressure Randall E. Youngman Science 345, 998 (2014); DOI: 10.1126/science.1258785
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Science (print ISSN 0036-8075; online ISSN 1095-9203) is published weekly, except the last week in December, by the American Association for the Advancement of Science, 1200 New York Avenue NW, Washington, DC 20005. Copyright 2014 by the American Association for the Advancement of Science; all rights reserved. The title Science is a registered trademark of AAAS.
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Genetics of rabbit domestication p. 1000
INSIGHTS
Tackling viral rebound to cure HIV infection p. 1005
PERSPECTIVES AMORPHOUS MATERIALS
Glimpsing glass structure under pressure Nuclear magnetic resonance spectroscopy of a glass under pressure adds to our understanding of network structure By Randall E. Youngman
998
PHOTO: COLLECTION OF THE CORNING MUSEUM OF GLASS, CORNING, NY. PURCHASED IN PART WITH FUNDS FROM THE MUSEUM ENDOWMENT FUND
A
rchaeologists suggest that the earliest known use of glass, natural obsidian, dates to the Stone Age, with extensive “modern” utilization as early as ~12,500 BCE (1). The first historical appearance of synthetic glass is around ~5000 BCE, where it was used as a glaze on clay and stone beads (2). Today, glass has broad uses in technology, architecture, packaging, and art. Throughout the technological (and artistic) advances in inorganic glasses, temperature has remained the single most important variable, controlling glass formation and playing a critical role in the short-range atomic structure of these disordered solids. On page 1027 of this issue, Edwards et al. (3) present findings on glass structure where pressure is the extrinsic variable. Using a novel nuclear magnetic resonance (NMR) methodology, they measured the boron-11 NMR spectrum of a borosilicate glass as a function of pressure in situ, in contrast to the more common postcompression analyses of glass. Their findings, augmented with ab initio calculations, demonstrate deformation of planar BO3 triangles, a key feature in boron-containing glasses, that leads to their eventual conversion to fourfold coordinated boron. Glass, given its widespread use, is a surprisingly complex material. Melt together sand, limestone, and soda ash, cool to room temperature, and you obtain soda-lime silicate glass—the most widely used glass in history. One of the attractive features of an inorganic glass-forming system (e.g., sodalime silicates or alkali borosilicates) is that it can be melted with a variety of inorganic compounds (e.g., to add color or to generate specific optical or physical properties)
Ancient glass art. A portrait of King Amenhotep II, Egypt (1426 to 1400 BCE) measures 4 cm high, 2.9 cm wide, and 3.4 cm deep.
sciencemag.org SCIENCE
29 AUGUST 2014 • VOL 345 ISSUE 6200
Published by AAAS
PHOTO: U.S. GEOLOGICAL SURVEY
and, with sufficiently rapid cooling, on the material. The simultaneous force the molten liquid to solidify combination of pressure and temwithout crystallization. The critiperature is unfortunately limited to cal cooling rate necessary for glass somewhat modest pressures (less formation depends on composition than 1 GPa), at least when work(4), and understanding glass-forming with samples of sufficient size ing tendencies for various inorganic for most property and structural systems has been critical in the decharacterization. velopment of glasses for optics, auThe work of Edwards et al. tomotive, and architectural uses, uncovers the mechanism of the as well as the recent application of conversion of threefold BO3 into glass in liquid-crystal display panfourfold BO4 that had previously els and as protective covers in conbeen studied at ambient condisumer electronics. tions as a function of cooling rate, However, the process of cooling or in glasses after being subjected the melt into glass is much more to high pressure. This glimpse into complicated, especially when other glass structure while under pressure components are included. For exmay signify the start of a new apample, glasses containing boron proach to understanding inorganic oxide (e.g., borosilicates), which glasses, even those that we have “unis typically added as a flux, have derstood” for centuries. Long-standshort-range atomic structures that ing limitations in understanding the are influenced by the cooling rate, effect of pressure on glass structure and thus the temperature, at which make the work of Edwards et al. that the melt solidified (5). The study much more remarkable in that these of structure-property relations has researchers have devised a comemerged as an important field in bined experimental and computatandem with the development of tional approach to study the boron methods to characterize glass strucenvironment of a borosilicate glass ture. One of the more mature and while maintaining the application of arguably most powerful techniques pressure. These types of experiments for glass structure determination is now begin to unveil the mechanisms NMR (6). Given the importance of A classic example of glass under pressure. Understanding glass structure of how liquids and glasses respond boron, silicon, aluminum, and other and dynamics as a function of temperature, pressure, or both is critical in to pressure. They hold great promise elements in glasses used in various development of glasses for high-technology applications and for advances in for understanding natural glasses technologies, NMR is particularly the geophysics of volcanology and magmas. and liquids, but also may generate well suited for study of glass netconsiderable interest in leveraging work structure and the effect of both temfor the same reason, but they also seek to pressure in the commercial glass industry. perature and pressure. leverage the structure-property relations in Work is already under way to investigate the The first of these variables, temperature, their materials to reduce warp, compaction, effect of pressure on key glass attributes (12), can be studied either directly by measurand other detrimental physical changes that but mechanistic understanding of the type ing NMR and other spectroscopic data as often accompany the heating and cooling described by Edwards et al. is an exciting a function of temperature, sometimes excycles that reset the thermal history of a and necessary contribution to understandceeding the glass transition temperature glass. ing an ancient material. ■ (where viscosity is 1012 Pa·s), or indirectly Pressure is another variable in materiREFERENCES through examination of glasses having als processing that has gained considerable 1. A. M. Pollard, C. Heron, Archaeological Chemistry (Royal experienced different cooling rates (e.g., traction in the glass science community. As Society of Chemistry, Cambridge, 2008). thermal history) (7). For both practical apwith temperature, the primary drivers of 2. K. Cummings, A History of Glassforming (A & C Black, London, 2002). plications and fundamental understanding, research into glasses and high pressure are 3. T. Edwards, T. Endo, J. Walton, S. Sen, Science 345, 1027 the temperature sensitivity of glass strucgeoscientists, constantly seeking a better un(2014). ture and related glass properties continues derstanding of volcanology and magmatic 4. P. I. K. Onorato, D. R. Uhlmann, J. Non-Cryst. Solids 22, 367 (1976). to captivate researchers. Glass scientists, processes (8, 9) (see the figure). In glass 5. J. F. Stebbins, S. E. Ellsworth, J. Am. Ceram. Soc. 79, 2247 and especially geochemists interested in science, pressure effects on structure and (1996). silicates, have gained useful understandproperties are generally studied on glasses 6. H. Eckert, Prog. Nucl. Magn. Reson. Spectrosc. 24, 159 (1992). ing of the temperature dependence of glass after application of pressure (i.e., postcom7. F. Angeli et al., Phys. Rev. B 85, 054110 (2012). and melt structures. In turn, these findings pression) (10). Recently, the development of 8. S. Webb, Rev. Geophys. 35, 191 (1997). have resulted in powerful new approaches high-temperature and high-pressure appa9. G. Calas, G. S. Henderson, J. F. Stebbins, Elements 2, 265 (2006). to optimize properties of glass. Glass artratuses has opened up research into glasses 10. S. K. Lee et al., J. Phys. Chem. C 116, 2183 (2011). ists anneal their finished work to eliminate cooled from moderate to high temperatures 11. M. M. Smedskjaer et al., Sci. Rep. 4, 10.1038/srep03770 thermal stresses and increase their durabilwhile under pressure (11). These types of (2014). 12. M. N. Svenson et al., ACS Appl. Mater. Interfaces 6, 10436 ity. Glass manufacturers might anneal glass experiments continue to provide new in(2014). sight into glass attributes, but only after application of pressure, where it must be Science and Technology Division, Corning Inc., Corning, NY 14831, USA. E-mail: [email protected] 10.1126/science.1258785 assumed that pressure had a lasting impact 29 AUGUST 2014 • VOL 345 ISSUE 6200
SCIENCE sciencemag.org
Published by AAAS
999
This copy is for your personal, non-commercial use only.
If you wish to distribute this article to others, you can order high-quality copies for your colleagues, clients, or customers by clicking here.
The following resources related to this article are available online at www.sciencemag.org (this information is current as of August 29, 2014 ): Updated information and services, including high-resolution figures, can be found in the online version of this article at: http://www.sciencemag.org/content/345/6200/998.full.html A list of selected additional articles on the Science Web sites related to this article can be found at: http://www.sciencemag.org/content/345/6200/998.full.html#related This article cites 10 articles, 2 of which can be accessed free: http://www.sciencemag.org/content/345/6200/998.full.html#ref-list-1 This article appears in the following subject collections: Materials Science http://www.sciencemag.org/cgi/collection/mat_sci
Science (print ISSN 0036-8075; online ISSN 1095-9203) is published weekly, except the last week in December, by the American Association for the Advancement of Science, 1200 New York Avenue NW, Washington, DC 20005. Copyright 2014 by the American Association for the Advancement of Science; all rights reserved. The title Science is a registered trademark of AAAS.
Downloaded from www.sciencemag.org on August 29, 2014
Permission to republish or repurpose articles or portions of articles can be obtained by following the guidelines here.
Genetics of rabbit domestication p. 1000
INSIGHTS
Tackling viral rebound to cure HIV infection p. 1005
PERSPECTIVES AMORPHOUS MATERIALS
Glimpsing glass structure under pressure Nuclear magnetic resonance spectroscopy of a glass under pressure adds to our understanding of network structure By Randall E. Youngman
998
PHOTO: COLLECTION OF THE CORNING MUSEUM OF GLASS, CORNING, NY. PURCHASED IN PART WITH FUNDS FROM THE MUSEUM ENDOWMENT FUND
A
rchaeologists suggest that the earliest known use of glass, natural obsidian, dates to the Stone Age, with extensive “modern” utilization as early as ~12,500 BCE (1). The first historical appearance of synthetic glass is around ~5000 BCE, where it was used as a glaze on clay and stone beads (2). Today, glass has broad uses in technology, architecture, packaging, and art. Throughout the technological (and artistic) advances in inorganic glasses, temperature has remained the single most important variable, controlling glass formation and playing a critical role in the short-range atomic structure of these disordered solids. On page 1027 of this issue, Edwards et al. (3) present findings on glass structure where pressure is the extrinsic variable. Using a novel nuclear magnetic resonance (NMR) methodology, they measured the boron-11 NMR spectrum of a borosilicate glass as a function of pressure in situ, in contrast to the more common postcompression analyses of glass. Their findings, augmented with ab initio calculations, demonstrate deformation of planar BO3 triangles, a key feature in boron-containing glasses, that leads to their eventual conversion to fourfold coordinated boron. Glass, given its widespread use, is a surprisingly complex material. Melt together sand, limestone, and soda ash, cool to room temperature, and you obtain soda-lime silicate glass—the most widely used glass in history. One of the attractive features of an inorganic glass-forming system (e.g., sodalime silicates or alkali borosilicates) is that it can be melted with a variety of inorganic compounds (e.g., to add color or to generate specific optical or physical properties)
Ancient glass art. A portrait of King Amenhotep II, Egypt (1426 to 1400 BCE) measures 4 cm high, 2.9 cm wide, and 3.4 cm deep.
sciencemag.org SCIENCE
29 AUGUST 2014 • VOL 345 ISSUE 6200
Published by AAAS
PHOTO: U.S. GEOLOGICAL SURVEY
and, with sufficiently rapid cooling, on the material. The simultaneous force the molten liquid to solidify combination of pressure and temwithout crystallization. The critiperature is unfortunately limited to cal cooling rate necessary for glass somewhat modest pressures (less formation depends on composition than 1 GPa), at least when work(4), and understanding glass-forming with samples of sufficient size ing tendencies for various inorganic for most property and structural systems has been critical in the decharacterization. velopment of glasses for optics, auThe work of Edwards et al. tomotive, and architectural uses, uncovers the mechanism of the as well as the recent application of conversion of threefold BO3 into glass in liquid-crystal display panfourfold BO4 that had previously els and as protective covers in conbeen studied at ambient condisumer electronics. tions as a function of cooling rate, However, the process of cooling or in glasses after being subjected the melt into glass is much more to high pressure. This glimpse into complicated, especially when other glass structure while under pressure components are included. For exmay signify the start of a new apample, glasses containing boron proach to understanding inorganic oxide (e.g., borosilicates), which glasses, even those that we have “unis typically added as a flux, have derstood” for centuries. Long-standshort-range atomic structures that ing limitations in understanding the are influenced by the cooling rate, effect of pressure on glass structure and thus the temperature, at which make the work of Edwards et al. that the melt solidified (5). The study much more remarkable in that these of structure-property relations has researchers have devised a comemerged as an important field in bined experimental and computatandem with the development of tional approach to study the boron methods to characterize glass strucenvironment of a borosilicate glass ture. One of the more mature and while maintaining the application of arguably most powerful techniques pressure. These types of experiments for glass structure determination is now begin to unveil the mechanisms NMR (6). Given the importance of A classic example of glass under pressure. Understanding glass structure of how liquids and glasses respond boron, silicon, aluminum, and other and dynamics as a function of temperature, pressure, or both is critical in to pressure. They hold great promise elements in glasses used in various development of glasses for high-technology applications and for advances in for understanding natural glasses technologies, NMR is particularly the geophysics of volcanology and magmas. and liquids, but also may generate well suited for study of glass netconsiderable interest in leveraging work structure and the effect of both temfor the same reason, but they also seek to pressure in the commercial glass industry. perature and pressure. leverage the structure-property relations in Work is already under way to investigate the The first of these variables, temperature, their materials to reduce warp, compaction, effect of pressure on key glass attributes (12), can be studied either directly by measurand other detrimental physical changes that but mechanistic understanding of the type ing NMR and other spectroscopic data as often accompany the heating and cooling described by Edwards et al. is an exciting a function of temperature, sometimes excycles that reset the thermal history of a and necessary contribution to understandceeding the glass transition temperature glass. ing an ancient material. ■ (where viscosity is 1012 Pa·s), or indirectly Pressure is another variable in materiREFERENCES through examination of glasses having als processing that has gained considerable 1. A. M. Pollard, C. Heron, Archaeological Chemistry (Royal experienced different cooling rates (e.g., traction in the glass science community. As Society of Chemistry, Cambridge, 2008). thermal history) (7). For both practical apwith temperature, the primary drivers of 2. K. Cummings, A History of Glassforming (A & C Black, London, 2002). plications and fundamental understanding, research into glasses and high pressure are 3. T. Edwards, T. Endo, J. Walton, S. Sen, Science 345, 1027 the temperature sensitivity of glass strucgeoscientists, constantly seeking a better un(2014). ture and related glass properties continues derstanding of volcanology and magmatic 4. P. I. K. Onorato, D. R. Uhlmann, J. Non-Cryst. Solids 22, 367 (1976). to captivate researchers. Glass scientists, processes (8, 9) (see the figure). In glass 5. J. F. Stebbins, S. E. Ellsworth, J. Am. Ceram. Soc. 79, 2247 and especially geochemists interested in science, pressure effects on structure and (1996). silicates, have gained useful understandproperties are generally studied on glasses 6. H. Eckert, Prog. Nucl. Magn. Reson. Spectrosc. 24, 159 (1992). ing of the temperature dependence of glass after application of pressure (i.e., postcom7. F. Angeli et al., Phys. Rev. B 85, 054110 (2012). and melt structures. In turn, these findings pression) (10). Recently, the development of 8. S. Webb, Rev. Geophys. 35, 191 (1997). have resulted in powerful new approaches high-temperature and high-pressure appa9. G. Calas, G. S. Henderson, J. F. Stebbins, Elements 2, 265 (2006). to optimize properties of glass. Glass artratuses has opened up research into glasses 10. S. K. Lee et al., J. Phys. Chem. C 116, 2183 (2011). ists anneal their finished work to eliminate cooled from moderate to high temperatures 11. M. M. Smedskjaer et al., Sci. Rep. 4, 10.1038/srep03770 thermal stresses and increase their durabilwhile under pressure (11). These types of (2014). 12. M. N. Svenson et al., ACS Appl. Mater. Interfaces 6, 10436 ity. Glass manufacturers might anneal glass experiments continue to provide new in(2014). sight into glass attributes, but only after application of pressure, where it must be Science and Technology Division, Corning Inc., Corning, NY 14831, USA. E-mail: [email protected] 10.1126/science.1258785 assumed that pressure had a lasting impact 29 AUGUST 2014 • VOL 345 ISSUE 6200
SCIENCE sciencemag.org
Published by AAAS
999
