Tobermorite, Ca5Si6O16(OH)2·4H2O, is a hydrous calcium silicate that has a layer-type of structure similar to that of the 2:1 clay minerals. In its natural form, tobermorite exhibits little or no exchange for alkali cations; synthetic tobermorites, however, exhibit reversible alkali cation exchange and selective cesium uptake upon a coupled substitution of (Al3+ + Na+) for Si4+. Substituted tobermorites were synthesized using aluminosilicate gels, NaOH, and CaO, in Parr bombs at 175°C for 4 days. Unsubstituted tobermorite was synthesized using quartz and CaO in a Parr bomb at 175°C for 20 hr. Two (Al + Na)-substituted tobermorites showed cation-exchange capacities (CEC) of 77 and 71 meq/100 g, whereas an unsubstituted tobermorite showed a CEC of 12 meq/100 g. The substituted tobermorites exhibited selective Cs exchange from either NaCl or CaCl2 solutions. For example, one substituted tobermorite showed a Cs-exchange coefficient (Kd) of 15,100, whereas unsubstituted tobermorite showed a Kd of only 90 from a 0.02 N CaCl2 solution containing 0.0002 moles/liter CsCl. Exchange isotherms for Na+ ⇋ Cs+ showed that Cs+ is preferred over Na+ throughout the exchange in the (Al + Na)-substituted tobermorites. This group of cation exchangers is expected to find applications in radioactive waste disposal.

Various Lamp phosphors, including [Ca10(PO4)6(Cl,F):Sb:Mn], (Y,Eu)2O3 (YOE), BaMgAl10O17:Eu (BAM), and (La,Ce)PO4:Ce:Tb (LAP), with or without flux, have been synthesized by a microwave processing technique in a multimode microwave furnace operating at 2.45 GHz. The microwave-synthesized phosphors were comprehensively characterized for particle size, specific surface area, brightness, and luminescence. Although most properties of the microwave-synthesized phosphors were comparable to that of the conventional products, the kinetics of the phosphor synthesis was substantially enhanced in the microwave processing. As a result, the soaking time at the final temperature was reduced by up to 90% compared to a conventional process. In addition, the required synthesis temperature was also lowered by 100-200°C in microwave process, compared to the conventional process for these lamp phosphors. Certain improved property was also observed in some microwave synthesized samples. The mechanism and advantages of microwave process for the lamp phosphor synthesis through solid-state reaction are addressed.

Highly doped n-type silicon powder responds aggressively to a 2.45-GHz microwave E-field, whereas it remains unperturbed in the H-field. In the E-field, after about 30 s of treatment, the silicon powder attained submelting temperatures and thus coagulated to a bulk solid piece. X-ray diffraction analysis of the surface and the cross section of this solid material failed to show any detectable peaks, ascertaining the fact that the material had decrystallized. The Raman spectra of the material had broad and shallow peaks quite different from the thin, sharp lines exhibited by Si wafer. It appears that the E-field treatment has considerably distorted the lattice structure creating lattice strains throughout the sample. These lattice strains were relieved by grinding (recrystallized).

Ultralow dielectric constant values were measured on Ni–Zn ferrites prepared using Fe2O3 as a starting material and sintered in a microwave field. Significant differences in microstructure, magnetic, and dielectric properties were observed between microwave-sintered Ni–Zn ferrites prepared using Fe3O4 (T34) and those starting with Fe2O3 (T23) ingredients. Higher magnetization values observed in T23 ferrite are attributed to large grain size, possibly containing abundant domain walls and the presence of fewer Fe2+ ions. The ultralow dielectric constant values observed on T23 ferrites show that this procedure is highly suitable to prepare Ni–Zn ferrites for high-frequency switching applications.

We demonstrate in this paper that common crystalline phases can be made noncrystalline and hard magnets can be converted to soft magnets in the solid state in several seconds at temperatures far below the melting points. New crystal structures and magnetic structures of ferromagnetic oxides (ferrites such as BaFe12O19, CoFe2O4, Fe3O4, and ZnFe2O4, etc.) are formed by reacting either the stoichiometric mixture of oxides or the preformed phase-pure crystalline material in a pure H field (or E field) at microwave (2.45 GHz) frequencies. These major changes in the magnetic properties as well as major structural phase changes are caused by the magnetic field.

Yttrium iron garnet (YIG) powder has been synthesized in just less than 10 min in a multimode microwave oven operating at 2.45 GHz. The simple solid-state synthesis involves an anisothermal reaction between a highly microwave absorbing Fe3O4 and a low microwave absorbing Y2O3 at temperatures of 1300 °C. The rapidity of the YIG formation suggests that the reaction rate is possibly enhanced by several times in a microwave field.

A variety of educational resources are available in the area of materials science and engineering. These resources are widely dispersed and are often hard to find. Several efforts to collect and categorize the wide variety of educational modules, demonstrations, laboratories and texts have been launched in recent years, but none have been able to incorporate the vast majority of resources. The current effort is funded by NSF and has been collecting information from a variety of sources over the past year. It is being integrated with the Materials Education Library project that has been under way at the University of Michigan since 1997. These projects will result in a fully searchable database, published both on the world wide web and in a print catalog, with the first edition being available by summer 2000. The draft web site may be found at http://msewww.engin.umich.edu/MEL/; a permanent web site will be available by the end of 2000.

Results are presented on the influence of the size of diamond powders and the laser power on the main Raman line. These results show conclusively that there is a consistent and systematic, reversible, downshift with both decrease of powder size, and increase of power. The shift can be explained by local heating of about 500 °C in the extreme case. Its significance applies to interpretation of the alleged “downshifting” of the 1332 cm−1 line in all diamond research. In the future, the grain size, the thermal contact, and the beam power must be carefully monitored in reporting and interpreting any frequency shifts.

Mechanochemical activation of solid inorganic precursors and sol-gel routes followed by hydrothermal treatment in the presence of surfactants were used to synthesize highly dispersed NZP-type complex zirconium phosphates. Genesis of samples real structure and its impact on the surface properties and catalytic performance in the reactions of hexane isomerization and dehydroaromatization have been studied.

Careless claims by scientists are often expanded further by journalists and grossly distort the scientific “truths” passed on to the public and policy maker. Recently, such overclaims have invaded the field of materials synthesis.

The real first principles of materials synthesis, based on the work of V.M. Goldschmidt (and Linus Pauling), have proved to be, and continue to be, very successful. By combining such principles with Edison's methodology of careful observation, precise experimentation and rapid feedback, thousands of new (inorganic) phases have been, and continue to be made (since 1948, several hundred from our own laboratory), producing dozens of useful, widely commercialized materials.

In contrast, in spite of seventy years of trying, the so-called “first principles” calculations (from the quantum mechanics of cores and electrons) have utterly failed to actually predict and synthesize a single new material or add anything to the deep and reliable insights of well known chemical theories. It is clear that what students and researchers in contemporary materials synthesis need most is a thorough grounding in crystal chemistry and phase equilibria (including metastable equilibria).

The history of the “C3N4” failure, as a harder than diamond candidate, is prototypical of the”calculating” approach to synthesis. It is contrasted with short summaries on four recent real advances into completely new processes for diamond synthesis.

Dense and translucent ceramics were prepared by sintering of cylindrical preforms of hydroxyapatite extruded from xerogels. Extruded specimens were dried as monoliths and then consolidated by applying cold isostatic pressure, ranging from 500 to 1500 MPa. Upon heating the samples began to densify at 610 °C, and the densification/sintering was completed at 870 °C as was evidenced by the dilatometry plot indicating no further shrinkage. The sintered specimens thus formed were translucent in appearance. Further heating of the samples up to 1200 °C resulted in their “bloating” or creation of pores in the originally dense matrix. Pore creation within the structure is reproducible, it proceeds from the surface to the interior of the sample, and its spreading can be thermally controlled. Pore evolution within the single phase dense polycrystalline material is not related to the frequently occurring phenomenon of microcracking in ceramics during cooling.

Carbon-carbon composites, if not suitably protected, suffer from the problem of oxidation of the surface in normal atmospheres at temperatures above 350 °C. For this reason they need to be protected from oxidizing environments by either using an impermeable coating, or using a sacrificial protective coating of a suitable material, and/or doping of an oxidation inhibitor in the carbon. In this study we have used a new family of materials with tailorable thermal expansion characteristics, namely, the [NZP] family as the materials for developing a suitable coating material for C-C composites. The candidates selected for matching thermal expansion with that of carbon are Ca0.5Sr0.5Zr4P6O24, SrZr4P6O24, and Ba1.175Zr4P5.65Si0.35O24. They can be sintered in inert atmosphere without decomposition of the phases, and can be hot-pressed in inert atmosphere with C-C composites at 1250 °C without decomposition or chemical interaction. They are stable in the presence of carbon up to 1200 °C for at least a period of 4 h. They also do not show any weight loss after exposure to various temperatures up to 1200 °C for 4 h.

We have compared the microwave-hydrothermal (M-H) processing with conventional hydrothermal (C-H) processing in the preparation of two layered anion exchangers, i.e., Mg3Al(OH)8NO3 · nH2O and Ni1-xZn2x(OH)2(CH3COO)2x · nH2O. Both these phases can be crystallized more rapidly (an order of magnitude) under M-H processing compared to C-H processing. The above layered mixed basic salt of Ni and Zn was found to exhibit very high selectivity for PO4= (Kd = 15,000). Its order of selectivity for various anions in the presence of 0.1 N̲ NaC1 (ratio of C1- to anion in question is 100) increases as follows: PO4= ≫ SO4= > NO3-.

Powder x-ray diffraction (XRD) and Raman evidence are presented for the formation of crystalline diamond in the “hydrothermal” pressure-temperature regime 1–5 kbars, <1000 °C. Two different methods appear to enable diamond to nucleate and grow. One—a Low Pressure Solid-State Source (LPSSS) route—utilizes special solid precursors, especially low temperature glassy carbon (GC-500), with very fine diamond seeds in sealed gold capsules with H2O at, say, 800 °C and 1 kbar. The other includes pyrolysis of highly selected organic solid/liquid precursors (halogenated aliphatics such as iodoform) onto similar diamond seeds. In all the cases, powder x-ray diffraction evidence shows a marked increase of the diamond XRD peaks, likewise the Raman spectrum shows a strong increase of the 1331 cm−1 line. However, the crystals apparently are too small to be seen in the SEM. TEM diffraction data, on the other hand, seem to lend support to the possibility of all the grown diamonds being very small.

The setting of the technical subsystem within the overall socio-political-economic-technical radwaste system will be described and the highly interactive nature of the larger setting emphasized. It will be shown that because of the dominance of the socio-political subsystem, the importance of the technical subsystem is overshadowed. Moreover the key issue in the technical subsystem, whether to put more reliance on the immobilization (via the waste package or engineeered barriers) or the isolation (via the geology) has stayed tilted toward the latter since 1978, when we organized the first symposium on radwaste science (at the Materials Research Society meeting). Now that the isolation strategy is stymied, the opportunity arises again for the materials community to make a compelling case for the waste package's true significance.

This review is made mainly from the perspective of one laboratory in one country, the U.S. What is remarkable about the state of research in the technical subsystem is how little the big picture of the science or the technology has changed after some billions spent on R/D. The borosilicate glass (almost unchanged) is still the establishment's choice of reference waste form for HLW Cost, however, is finally forcing cement encapsulated forms to be given a second look. Mineral-modeled ceramics have received a great deal of scientific attention but remain esoteric to managers. It will be shown that in the author's opinion an enormous amount of detailed science has been done but most of it is unlikely to prove to be of any relevance or use. The policy implications for future R/D are discussed.

Condensed silica fume, a by-product from the production of silicon alloys, was sintered by (i) conventional heating in a dilatometric furnace, both at constant heating rate and isothermal heating, and (ii) by the microwave heating. The dense products with relative density up to 95% of theoretical can be obtained only by short runs at high heating rates, preferentially accomplished by the microwave treatment. Prolonged heating leads to the devitrification of the original glassy phase to cristobalite, accompanied by an arrest of densification.

Novel microwave-hydrothermal processing has been developed by us recently for the synthesis of a wide variety of ceramic powders. Herein, we report the use of microwave-hydrothermal processing to synthesize several metal powders such as Cu, Ni, Co, and Ag by reducing their corresponding metal salts or hydroxides with ethylene glycol. Metal powders have been produced extremely rapidly a (few minutes) by microwave catalysis. The kinetics of metal powder synthesis have been increased by at least an order of magnitude by microwave-hydrothermal processing compared to the conventional refluxing process in ethylene glycol at about 195 °C.

Ca0.5Sr0.5Zr4P6O24 (CSZP) powders were prepared by the decomposition/combustion method using Ca(NO3)2 · 4H2O, Sr(NO3)2, ZrO(NO3)2 · xH2O, NH4H2PO4, urea, and NH4NO3 as starting materials. The homogenized slurries of the mixture were heated at 500 °C for 5 min to obtain CSZP powders. The as-synthesized powders were amorphous and crystallized after heating 800 °C for 2 h. The specific surface area of the powder was varied with the batch weight of starting materials or the amount of urea and ammonium nitrate. Powders with high specific surface area (150 m2/g) could be produced by this method. The sinterability of the powders was comparable to that of sol-gel derived powders. The sintered density of the compacts was 99% of theoretical after firing in air at 1350 °C for 6 h.

A review and some case studies on the interatomic distances of candidate substrates in comparison to the high Tc superconductor (HTSC) phase YBa2Cu3O7−δ (YBCO) is presented, in an attempt to enhance the basis for substrate selection for YBCO film epitaxy. This preliminary study was carried out by examining a variety of interatomic distances in the structure rather than merely matching the lattice parameters. Interatomic structure matching planes of selected YBCO orientations in contact with substrates were identified. The surface termination of the substrate was found to be a crucial parameter in determining the oriented or epitaxial growth. Possible composition dependence of the orientation of the films at the nucleation stage was also anticipated depending on the comparison. Several currently most commonly used substrates are discussed in some detail.