Joseph Kolis - US grants

This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is concerned with the chemistry of the so-called post transition elements, which include selenium, tellurium, arsenic and tin. Anionic clusters of these elements, i.e. clusters of atoms with negative charges, have been known for some time, but little is known about the chemistry of these clusters. The focus of the project is the reactions of these clusters with transition metals, such as chromium and niobium, to form a variety of unusual new mixed-element clusters. The new species are of interest because they are soluble precursors of new materials, and because they pose interesting challenges to existing bonding theories. The reactions of post transition element cluster anions, such as the triselenide, the tetratelluride and the nonastannide ions, with transition metal complexes will be investigated. The goal is to prepare new cluster anions containing both transition and main group elements. Strategies will be developed for stabilizing the cluster anions in solution, such as the introduction of carbon as a heterovertex atom. For the preparation of the target clusters the reactions of main group anionic clusters with transition metal halides and with a variety of organometallic compounds will be investigated.

With funding from the Organic Dynamics Program Professors Parson and Kolis of Clemson University will develop new routes to the synthesis of commercially important chemicals using supercritical water as a solvent. This environmentally benign synthesis proposal emphasizes the scope and mechanisms of metal catalyzed oxidations of small organic molecules in supercritical water. A collaborative effort with Professor Myrick at the University of South Carolina will involve in situ Raman spectroscopy monitoring of the reactions taking place in supercritical water. Eastman Kodak will offer advice by identifying critical needs for better methods to produce industrially important compounds. This research will address an area of strategic importance in the chemical industry. The project will explore the fundamental chemistry that occurs when small carbon containing compounds are oxidized in a reactor using supercritical water( a unique form of water at high temperature and pressure) in the presence of metal ion catalysts. The use of supercritical water to replace organic solvents shows promise in the reduction of environmental pollution and the generation of hazardous wastes.

This award from the Chemistry Research Instrumentation and Facilities (CRIF) Program will assist the Department of Chemistry at Clemson University acquire a superconducting quantum interference device (SQUID) magnetometer. This equipment will enhance research in areas which will include inorganic chemistry, magnetochemistry, solid state materials, magnetic nanoclusters, conducting polymers, superconductivity, thermoelectrics, and colossal magnetoresistance. The superconducting quantum interference device (SQUID) magnetometer measures very small currents or voltages and permits precise magnetic measurements of materials.

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research by Dr. Joseph W. Kolis, Chemistry Department, Clemson University, for the study of novel synthetic methods for transition metal-main group solids. The relatively low reaction temperature of supercritical fluids permits isolation of kinetically stabilized phases not otherwise easily obtainable. Solids of the general formula AxMyEz, where A=alkali metal, M=Cu, Ag, and E=S, Se, will be prepared in supercritical ammonia or ethylenediamine. Attempts will also be made to use bismuth and tellurium. The resulting compounds are expected to have low dimensional structures and potentially interesting electronic properties. A dominant strategy for the synthesis will be to replace monovalent alkali metals with divalent cations, or replacement of monovalent coinage metals with open shell transition metals such as manganese (II) or iron (II). In addition, new techniques will be developed for some unusual aqueous solvents. Hydrothermal brines with high concentrations of halides, sulfides or carbonates will be used to synthesize new metal chalcogenides under conditions similar to those under which naturally occurring gems and minerals form. Solid state compounds are useful in electronic devices, so development of new materials and new methods to prepare materials are important areas of research. The new methods to be developed with the support of this award not only are novel and may result in useful new solids, but may have implications for understanding formation of minerals in nature as well

This project will exploit techniques recently developed by the PI at Clemson University for the efficient, high throughput investigation of new solids from high temperature hydrothermal solutions (up to 600 degrees C, and 3 kbar). These reactions often lead to high quality single crystals of new compounds that are otherwise difficult or impossible to prepare by any other technique. Many of these materials have very interesting optoelectronic properties. Specific emphasis will be placed in compounds crystallizing in acentric or polar space groups. The chemistry of metal complexes of several interesting oxyanion building blocks will be investigated, including borates, germanates and vanadates. New metal fluoride will also be investigated as well as several new fluoride-based building blocks such as BeF42- that show exceptional promise as reagents for new wide bandgap acentric solids. This work has substantial impact in terms of training of students particularly in specialty crystal growth. The growth of device quality crystals induces students to become involved with numerous collaborators, especially in industrial labs, using their new materials in real applications. This allows students to confront many of the issues they will face in their professional careers. This work has already led to the development of several short courses and tutorials, such as one for the NSF Solid State Chemistry Undergraduate Summer Program.
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Many of these high quality crystals of new compounds have very interesting optical properties and can be used in next generation lasers, high-density data storage and high-speed optical communication. The technique mimics the methods used by nature to grow gems such as rubies and emeralds. This work has substantial impact in terms of training of students particularly in specialty crystal growth, a subject that is almost ignored in US university chemical curricula. It also induces students to become involved with numerous collaborators, especially in industrial labs, using their new materials in real world applications. This intimate exposure to real world industrial applications forces the students to develop the kinds of team oriented problem solving they will confront in their professional life. The development of several short courses and tutorials, such as one for the NSF Solid State Undergraduate Summer Program is having significant impact in meeting educational needs by providing new curricula. This project is jointly supported by the Chemistry Division and the Division of Materials Research.
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Planning Grant for an I/UCRC for the Ceramic, Composite and Optical Materials Center

0934300 Clemson University; Dennis Smith
0934258 Rutgers University; Richard Haber

The Center for the Ceramic, Composite and Optical Materials Center (CCOMC) will focus on providing a broader range of relevant technologies critical to materials-based companies. Clemson University and Rutgers University are collaborating to establish the proposed center, with Clemson University as the lead institution.

The Center for Ceramic Research (CRC) at Rutgers University, a past member of an ending NSF I/UCRC for Ceramic and Composite Materials Center, proposes to join with the Center for Optical Material Science and Engineering Technologies (COMSET) at Clemson University to form the proposed new Center (CCOMC) with new technological thrusts. COMSET has developed a strong industrial base, with three spin-off companies that, combined with Rutgers University, would provide a new and unique research program. The proposed Center (CCOMC) will focus on five thrust areas including ceramic materials and processing, nanoparticulates and processes, opaque and transparent armor ceramics, optical material synthesis and processing, and materials for energy conversion. The proposed research program across the five thrust areas will be carried out by an interdisciplinary group of faculty and across different academic disciplines. The PIs are well-qualified and have adequate resources to conduct the proposed research. Both institutions in this Center plan to use the NSF planning grant fund to hold a meeting with prospective industrial partners to establish the proposed Center's organizational framework, and to establish research projects of greatest relevance.

The proposed center (CCOMC) has the potential to improve sustainability and profitability of US manufacturing by developing new technologies in the ceramic, optic and composite material field. CCOMC has plans in place for involving under-represented groups, to recruit highly qualified faculty and graduate students, and to motivate undergraduate students through unique research experiences and fellowships. Results will be disseminated through semi-annual meetings, publications, and a website for information, results and accomplishments. CCOMC will continue to integrate research and education; and by providing hands-on experience to students, the Center will attempt to motivate students to go beyond common approaches towards learning by hands-on experiences in state-of-the-art facilities focusing on today's relevant materials issues.

TECHNICAL SUMMARY:
This new proposal outlines plans to exploit the hydrothermal method to explore new categories of materials with particular emphasis on extremely refractory oxides. The hydrothermal method employs water at extremely high temperatures and pressures and has proven to be an excellent technique for the preparation of a wide variety of inorganic materials as high quality single crystals. Technology was developed at Clemson to do reactions at substantially higher temperatures (750¢ªC) with more powerful and concentrated mineralizers (e.g.>25M hydroxide or halide) than any previously work in these labs. These conditions enable synthesis and good crystal growth on chemical systems heretofore too inert or refractory to be otherwise accessible. The specific categories of solids to be investigated are; 1) wide bandgap oxides, specifically the s block metal borates and beryllates; 2) ultrarefractory oxides like hafnates, thorates and yttrates; and 3) large single crystal ferromagnetic oxides for neutron diffraction study. The fundamental reaction chemistry will be systematically explored for each class of materials. Single crystals will be targeted in all cases. Our crystal growth can be divided into three broad regimes, namely crystals large enough for single crystal diffraction (0.3mm), crystals large enough for single crystal magnetic and piezoelectric characterization (1-2mm), and crystals large enough for optical device characterization (1cm). Each of these size regimes will employ an appropriate hydrothermal growth method. For example, for wide bandgap oxides to find use in deep UV optical applications, single crystals of 1 cm/edge will be required for characterization in prototype optical devices. In contrast, ferrimagnets specifically grown for single crystal magnetic structures on the nearby Oak Ridge Spallation Neutron Source will require single crystal 1-2 mm per edge.

NON-TECHNICAL SUMMARY: This work will employ a relatively obscure technology to grow single crystals of solids that are otherwise difficult to study. The solid crystals will have applications in many advanced technologies, especially lasers, advanced optics, magnetic materials and sensors. The field of crystal growth has all but disappeared from university research programs in the United States. This shortcoming has created a major gap in the skill set of onshore materials science capabilities. There is substantial evidence that this shortcoming is having a significant impact on national competitiveness in key materials. Furthermore this shortcoming has a significant negative impact on the students¡¯ research abilities. This is detrimental to scientific research and discouraging to students. A rational and systematic ability to grow crystals of sufficient size and quality for physical property evaluation leads to a dramatic improvement in the breadth of student development. Often patents result from this work and the resultant commercial application provides an important perspective to the students who are much thus better prepared to make better decisions about experimental design. Finally the technology is very ¡°green¡±, which raises the awareness of the students to societal impact of their science.

I/UCRC for the Ceramic, Composite and Optical Materials Center

1034979 Clemson University; Dennis Smith
1034978 Rutgers University; Richard Haber

The Center for the Ceramic, Composite and Optical Materials Center (CCOMC) will focus on providing a broader range of relevant technologies critical to materials-based companies. Clemson University and Rutgers University are collaborating to establish the proposed center, with Clemson University as the lead institution.

The Center for Ceramic Research (CRC) at Rutgers University, a past member of an ending NSF I/UCRC for Ceramic and Composite Materials Center (CCR), proposes to join with the Center for Optical Material Science and Engineering Technologies (COMSET) at Clemson University to form the proposed new Center (CCOMC) with new technological thrusts. COMSET has developed a strong industrial base, with three spin-off companies that, combined with Rutgers University, would provide a new and unique research program. The mission of the proposed Center (CCOMC) is to develop new innovations that enable and sustain United States competitiveness in ceramic, particulate, composite and optical material science, technology and engineering. Furthermore, the CCOMC will transfer these new innovations to its industrial members for competitive reproducible ceramic, particulate, composite and optical materials, for advanced, high performance commercial products. The proposed center's research projects are integrated into five thrust areas: powder synthesis and processing, nanoparticulates and processes, optical material synthesis and processing, materials for defense sciences, and materials for energy conversion. The proposed research program across the five thrust areas will be carried out by an interdisciplinary group of faculty and across different academic disciplines. The PIs are well-qualified and have adequate resources to conduct the proposed research.

The proposed center (CCOMC) has the potential to improve sustainability and profitability of US manufacturing by developing new technologies in the ceramic, optic and composite material field. CCOMC has plans in place for involving under-represented groups, to recruit highly qualified faculty and graduate students, and to motivate undergraduate students through unique research experiences and fellowships. Results will be disseminated through semi-annual meetings, publications, and a website for information, results and accomplishments. CCOMC will continue to integrate research and education; and by providing hands-on experience to students, the Center will attempt to motivate students to go beyond common approaches towards learning by hands-on experiences in state-of-the-art facilities focusing on todays relevant materials issues.

NON-TECHNICAL SUMMARY:
This project develops techniques to grow large single crystals of important materials for use in optics that are otherwise difficult to prepare and study. Many of the efforts focus on a fundamental study of fields such as new laser materials. These materials will add to the basic scientific understanding of new laser applications, new display technologies and new detector science. The primary support will be for the training of graduate students particularly those working toward the Ph.D. degree. They are being trained to perform research in crystal growth, characterization and properties of new materials for optical applications, an area that is generally underdeveloped in the US. Student interactions with industrial and national laboratory collaborators will be supported. The broader impacts of this work will enhance the expertise of the next generation of materials and expand the capacity of US researchers in optics and lasers.

TECHNICAL SUMMARY:
With support from the Solid State and Materials Chemistry program in the Division of Materials Research, this project employs the use of hydrothermal fluids, namely aqueous phases between 500-700 C and 1-2kbar for fundamental explorations of new solids. These conditions provide a unique medium for the exploratory growth of new materials, particularly in the form of large, high quality single crystals. This program focuses in particular, on single crystals that can serve as hosts for optical applications including lasing, up-conversion and scintillation. The emphasis is on metal oxides and halides that can be selectively doped with optically active ions. The goal is to discover and identify new phases that can be made in this unique reaction medium, and to study their structural and spectroscopic properties. There are three broad thrust areas under investigation, the novel chemistry of beryl-based oxides, the host chemistry of vanadates, and the fundamental exploratory chemistry of metal tantalates and niobates. In all cases, new structural types will be sought and their subsequent spectroscopic and optical properties will be investigated.

Non-Technical Summary<br/><br/>This project, supported by the Solid State and Materials Chemistry Program in NSF’s Division of Materials Research, will allow researchers at Clemson University to focus on the synthesis of new materials displaying unusual optical and magnetic properties. Particular emphasis is placed on the growth of high-quality single crystals in high temperature, high pressure water (the so-called high temperature hydrothermal method) that enables accurate characterization of complex physical properties such as magnetic structures. The target materials can display nonlinear optical or frustrated magnetic behavior which can lead to new quantum materials and enable a more detailed understanding of the compounds used in quantum computing and quantum communication. The project pays particular attention to the development of the next generation of researchers, supporting graduate students, undergraduates and postdoctoral fellows. It will also specifically educate new researchers on the targeted growth of single crystals, an area of considerable current need in the United States. Another important activity involves significant student collaboration with the state-of-the-art neutron and magnetic research facilities at Oak Ridge National Lab. These interactions with an advanced national laboratory provide invaluable learning experiences for the next generation of researchers.<br/><br/>Technical Summary<br/><br/>As part of this project, supported by the Solid State and Materials Chemistry Program in NSF’s Division of Materials Research, researchers at Clemson University will focus on the synthesis and characterization of new materials with interesting magnetic and nonlinear properties. The use of a high temperature hydrothermal method leads to the efficient growth of high quality single crystals with minimal lattice defects and negligible site disorder, which will enable accurate determination of physical properties. One specific goal is to gain a greater understanding of systems with coupled physical properties, such as multiferroics and magnetoelectrics. Emphasis will be on materials with potential magnetic frustration, especially those with low dimensional (1-D or 2-D) structures, so as to generate different intra- and interchain coupling of magnetic vectors. Such couplings can induce standing electric dipoles and perpendicular magnetic vectors leading to magnetoelectrics. This project will attempt to generalize the factors that cause such multiferroic behavior and design and synthesize new systems displaying more complex coupling. One important factor in the program is the collaboration with the neutron scattering facilities Oak Ridge National Lab. The initial focus will be on the elastic neutron scattering measurements to determine the static magnetic structures, followed by more complex inelastic measurements to determine coupling values. The ability to grow large single crystals is particularly important to understand the behavior of the magnetic structures in externally applied magnetic fields.<br/><br/>This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.