Colored glasses: the eye's pleasure and much more.

Georges Calas*, Laurence Galoisy, Laurent Cormier & Gérald Lelong

Institute of Mineralogy, Physics of Materials and Cosmochemistry, University Pierre and Marie Curie and CNRS, Paris, France

Since the discovery of glass making, the coloration caused by transition elements has always been one of the most attractive properties of glasses. Still now, transition metal ions constitute the most important source of glass coloring agents. Coloration varies, for a given transition element, as a function of chemical and physical parameters such as glass composition or melting/fining conditions. At the same time, the electronic transitions responsible for light selective absorption and glass coloration provide unique information about the local structure and chemical bonding of glasses. This presentation aims to review optical absorption data at the light of complementary information provided by a broad range of experimental and numerical structural approaches, providing a unique harvest of results: unusual coordination numbers as 5-fold coordination, distribution of site geometry, sensitivity to the chemical bond, medium-range organization, heterogeneous spatial distribution… Some of these structural characteristics are inherited from the peculiar dynamics of silicate melts and may show a significant modification as a function of temperature. As transition elements can be connected to the various structural subsets of glasses, they are useful color indicators of the complex structure of these materials. Vice versa, using a better knowledge of the structural behavior of transition elements, the variation of colors may be rationalized as a function of glass composition and melting conditions.

Profile

Georges Calas, FSGT, member of Academia Europaea, is Institut Universitaire de France Chair of Mineralogy, Université Pierre & Marie Curie-Paris. He will be the 2014-2015 Chair of Durable Development at College de France. Research activities include the structural organization and structure-property relationships in glasses and melts, with a special attention to transition elements. Other topics concern the chemical properties of technological glasses, the coloration of materials, the defect generation and durability of nuclear glasses and the environmental and industrial mineralogy, including the durability of raw materials resources.

----------------------------------------------

Modern Techniques: Aerolevitation, Time of Flight Mass Spectrometry, and Bactericidal Glasses

Mario Affatigato*, Steve Feller

Center for the Study of Glass and Physics DepartmentCoe College, 1220 First Av. NE Cedar Rapids, Iowa 52402 

 This presentation will summarize the research work carried out by Prof. Affatigato and his undergraduate students over the past eighteen years.  It will focus on some highlighted projects, namely: the determination of glass structure using laser ionization time of flight mass spectrometry; studies of glass modification by laser irradiation; bactericidal glass; and, most recently, glass manufacturing by aerolevitation and glasses for particle detection.  The work on mass spectrometry will cover a broad range of oxide glass systems, including the borates, borosilicates, germanate, and gallate families.  It has provided novel insights into the structure of glasses at intermediate length scales, measurements that are hard to obtain by any other techniques.  The studies of glass structure modification will primarily center on vanadate glasses, which also form the basis for more recent electronic conductivity work at the heart of new particle calorimeter detectors.  Bactericidal glass illustrates a nice collaborative project that involved simple borate glasses and helped pioneer their use in the human body—work that has led to significant medical developments by other colleagues and researchers.  Finally, the aerolevitation project gives new insight into the crystallization and property behavior of glasses and melts at very high temperatures (from 2000 °C to 3000 °C), as well as opportunities for new crystal formation.            The work by Prof. Affatigato and his students has been supported, over the years, by grants from the Research Corporation, the Petroleum Research Fund, private companies and foundations, and, primarily, by the U.S. National Science Foundation through its Ceramics, RUI, MRI, REU, and International programs.ProfileProf.

Profile

Mario Affatigato obtained his undergraduate degree from Coe College in 1989, followed by his Ph.D. from Vanderbilt University in 1995.  After returning to Coe that same year, he began a research effort investigating the relationship between the optical properties and structure of glassy materials.  The work he continues with his students (over 70 to date) has expanded into laser-induced modification and exotic manufacturing methods like aerolevitation.   His research primarily deals with oxide glasses, especially vanadates, borates, and samples with heavy metals.  Prof. Affatigato is a past recipient of a PECASE award from the National Science Foundation (NSF), as well as other research grants from NSF and various agencies in support of his work.  He is an active member of the American Ceramic Society, where he is a Fellow and past chair of the Glass and Optical Materials Division, the American Physical Society, and the Society of Glass Technology, of which he is a recent Fellow.  Currently he is the Fran Allison and Francis Halpin Professor and chair of the Physics Department.

-------------------------------------

Manufacturing High Purity Chalcogenide Glass

Daniel William Hewak, Kevin C C Huang, Khouler Khan, Paul Bastock,
Chris Craig and Edwin Weatherby

Optoelectronics Research Centre, University of Southampton, Southampton SO17 1BJ

Chalcogenide materials are finding increasing interest as an active material in next generation optical and electronic devices.  There wide range of properties, ranging from photosensitivity, ability to host rare earth ions, electrical conductivity, phase change, exceptional optical non-linearity’s to name only a few are fueling this interest.  Moreover, the ability to synthesize these materials in numerous forms as diverse as 2D monolayers, microspheres, optical fibres, nanowires, thin films as well as bulk glass ingots of over a kilogram in size ensures their application space is vast.

We began preparation of chalcogenides, largely based on sulphides, in 1992 and since then have built up an extensive capability for their purification, synthesis and fabrication in various forms.   A key aspect of this facility is the ability to process in a flowing atmosphere of hydrogen sulphide which provided the capability of synthesis from elemental, oxide or halide precursors, processing through various chemical vapour deposition reactions as well as post purification. 

In this talk we describe the range of materials we synthesize highlighting high purity sulphide bulk glass and transition metal di-chalcogenides for electronic applications, crystalline semiconductors for solar cell applications, low power phase change memory devices, switchable metamaterial devices as well as traditional chalcogenides glass and optical fibre.

Profile
Prof Dan Hewak leads a research group investigating novel glasses for optoelectronic devices. He obtained his PhD from the University of Waterloo, Canada, in 1989, where he studied planar optical waveguides and devices. He spent three years with the National Optics Institute in Quebec City before joining the ORC where his work on optical materials was funded by IBM and Digital Equipment Canada. Since 1991 he has been with the ORC where he has developed a broad range of experience in new optoelectronic materials, and in particular amorphous chalcogenides. In the past five years DH has worked on 10 major projects, 6 as project leader and participated in 8 EPSRC funded projects as a principle and co-investigator.  Relevant past EPSRC funded work includes integrated microsphere circuits, from which the world’s first chalcogenide glass microsphere and microsphere lasers emerged, optical and electronic phase change memory and work on advancing the applications of chalcogenide glass and photonic devices.  He has published over 250 refereed papers and conference publications and is the holder of eleven patents for novel glasses and their applications. He has presented his work internationally as both invited and contributed talks. DH has an extensive network of UK and international collaborators, both in academia and industry and serves on the TC20 Committee of the International Congress on Glass.  He is editor of IEE published textbook: ‘Properties, Processing and Applications of Glass and Rare-Earth Doped Glasses for Optical Fibres’ and serves on the Editorial Board for the Journal of Materials Science: Materials in Electronics.

----------------------------

The Advancements in Solid State NMR Experimentation, Methodologies and Instrumentation Impacting Upon Glass Science and Technology

John V. Hanna Department of Physics, University of Warwick

The solid state NMR technique has evolved remarkably over the last 10 - 20 years. Since its initial conception in the post-war period and into the 1950's, it undertook a long period of evolutional technical development and consolidation which allowed the scientific community to evaluate the information that it provided, and reconcile this data against other characterisation techniques such diffraction, microscopy and the vibrational spectroscopies. However, the more recent proliferation of higher magnetic field strengths, improved console characteristics (receiver sensitivity, rf stability, pulse programming flexibility) and enhanced probe capabilities (pulse power handling, MAS spinning frequencies) has truly enabled the solid state NMR technique to tackle more difficult/demanding materials and structural chemistry problems. In addition, the inception of exciting state-of-the-art sensitivity enhancement experiments such as dynamic nuclear polarisation (DNP) has facilitated the observation of insensitive nuclei and very low concentration bulk and surface species to unprecedented levels. One field of research that has benefitted greatly from all of these developments is glass science and technology. This presentation it will demonstrate aspects of how these improvements to the solid state NMR technology contributes routinely to glass and disordered material research in Millburn House. The Materials Solid State NMR Group at Warwick conducts programs of research into phosphate glass, bioglass/biocement and paramagnetically doped chalcogenide gallium sulphide systems (amongst others), with these modern solid state NMR approaches being crucial in elucidation and understanding of the structure-function relationships in these materials. To conclude, aspects of the DNP technique will be discussed and how large sensitivity enhancements derived from this experiment will impact upon glass science and technology in the future.

Profile

John Hanna obtained his BSc degree (physical and inorganic chemistry) from the University of Western Australia, and subsequent BSc (Hons.) and postgraduate degrees (chemical physics) from Griffith University. He managed the Brisbane NMR centre over the period of 1987-1989, and then went on to Direct the CSIRO North Ryde Solid State NMR and ASNTO Solid State NMR Facilities over the twenty year period 1989 - 2008. Since November 2008 he has been Principal Research Fellow and leader of the Materials Solid State NMR Group in the Centre for Magnetic Resonance in Millburn House at Warwick. His research interests centre on the application of solid state NMR techniques to glass and bioglass systems, inorganic oxide-based materials used in solid oxide and proton conduction fuel cell systems, battery systems, conventional and geopolymer cements, and homogeneous/heterogeneous catalysis. He has a particular focus on incorporating and rationalising solid state NMR data with structural information derived from other characterisation methods (particularly diffraction), and he is heavily involved with the use and development of DFT computation of NMR parameters to constrain structural information and generate 'NMR crystallography' formalisms. John currently sits on the User Executive Committee within EMSL at Pacific Northwest National Laboratories.

----------------------------

Chemical Evidence for Production and Trade of Islamic glass along the Silk Road
J. Henderson1, S. Chenery2, J. Kröger3, J. Evans2, E. Faber1 and S Bertier4.

1. Department of Archaeology, School of Humanities, University of Nottingham, University Park,                     Nottingham, NG7 2RD, UK
2The British Geological Survey, Keyworth, Nottinghamshire, NG12 5GG, UK; [email protected]
3. Bodestraße 1-3, 10178 Berlin, Germany
4. L.A.M.M., Aix en Provence, France

Scientific analysis of Islamic Middle Eastern glasses has mainly foced on major and minor elemental analysis and on isotopic analysis. These approaches have provided information about the raw materials used to make the glasses and about provenance respectively.

This paper will focus on new information that trace element analysis of glasses found on the Silk Road sites can provide. Results for glass samples selected from Silk Road sites between Egypt and Iran will be discussed. There is limited evidence for the primary production of plant ash Islamic glass. Our aims are to suggest the locations of primary production zones and/or sites and to investigate glass trade between them by using trace element analysis.

Ninety-eight glass samples were obtained from Cairo (Egypt), Khirbat al-Minya (Israel), Beirut (the Lebanon), Damascus (Syria), al-Raqqa (Syria), Samarra (Iraq), Ctesiphon (Iraq) and Nishapur (Iran) dating to between the 9th and 14th centuries.

Major and minor components were determined using a Jeol JSM 8200 Superprobe (electron probe microanalysis) housed in the microanalysis research facility in the Archaeology Department at Nottingham University. Trace elements were determined using LA-ICP-MS; a NewWave UP193FX excimer (193nm) laser coupled to an Agilent 7500 series ICP-MS at the British Geological Survey, Keyworth, Nottinghamshire.

Trace elements associated with both silica and plant ashes have provided clearer contrasts between Levantine, Syrian and Iraqi/Iranian production zones than identified by using major and minor and a restricted number of restricted elements (Kato et al. 2010, Henderson 2013, 294-297). Within these broad production zones trace element analysis has, for example, revealed the use of separate silica sources used in glass found on the relatively close Iraqi sites of Ctesiphon and Samarra. One interpretation for this is that the glasses were separate melts. The scientific results have provided clear evidence for separate production zones, trade in glass (vessels) between the Levantine coast and Iran (Nishapur) and for relationships between different types of glass vessels and chemical compositions.

Henderson, J. 2013. Ancient Glass: an interdisciplinary exploration, Cambridge: Cambridge University Press.

Kato, N., Nakai, I. and Shindo, Y. 2010. Transitions in Islamic plant ash glass vessels: On-site
chemical analyses conducted at the Rayaal Tur area on the Sinai Peninsula, Egypt, Journal of
Archaeological Science 37: 1381–95.

Profile

Following positions in Oxford and Sheffield Universities, since 2000 Julian Henderson has been Chair of archaeological science at Nottingham University. Since obtaining a PhD in physics he has focused on ancient glass technology, characterisation and provenance using a range of scientific techniques in collaboration with colleagues in the UK and abroad. His most recent book, Ancient Glass, is an interdisciplinary investigation of glass.