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Reactions of the Refractory Silicides With Carbon and With Nitrogen

Description: Abstract: The silicides of Ti, Zr, Ce and Nb were investigated to determine the phases present at temperatures around 2000 K. The reactions of silicides of Ti, Zr, Ce, Nb, Ta, Mo, and W with carbon were studied at these temperatures. Also a limited amount of work was done on the reactions of some of the silicides with nitrogen. The data have been used to establish ternary phase diagrams for the systems and to obtain upper and lower limits for the heats of formation of the silicides.
Date: April 29, 1954
Creator: Brewer, Leo, 1919-2005 & Krikorian, Oscar
Partner: UNT Libraries Government Documents Department

The Stereochemistry of Silenes and Alpha-Lithio Silanes

Description: When E- or Z-l-methyl-l-phenyl-2-neopentylsilene was generated by the retro-Diels-Alder vacuum-sealed tube thermolysis of its corresponding anthracene adduct, in the presence of various alkoxysilanes, only one diastereomeric adduct was formed in each case, showing that the reactions are stereospecific. An x-ray crystal structure of the methoxytriphenylsilane adduct of the E-silene confirmed its relative configuration as (R,S) or (S,R). This demonstrated that the addition of alkoxysilanes to silenes is stereospecific and syn. The relative configurations of similar alkoxysilane and alkoxystannane adducts to E- and Z-l-methyl-l-phenyl-2-neopentylsilene were assigned based on a combination of xray structures and *3C NMR data. A strong, nonbonded oxygen-metal interaction is apparent in all of those compounds studied. Treatment of the alkoxystannane adducts with alkyl lithium reagents results in tin-lithium exchange in some cases. The results indicate that the resulting <x-lithio alkoxysilanes are not configurationally stable in either THF or hydrocarbon solvents. The reaction of tert butyl lithium with a-trimethylsilylvinylmethylphenylchlorosilane in hydrocarbon solvents yields E- and Z-l-methyl-l-phenyl-2-neopentyl-2-trimethylsilylsilene. In the absence of any traps these silenes undergo a novel tert butyl lithium catalyzed rearrangement to 2-phenyl-3-trimethylsilyl-5,5-dimethyl-2-silahex-3-ene. These silenes were also trapped as their [4+2] cycloadducts with anthracene. The Z-isomer of the anthracene adduct was separated and its stereochemistry confirmed by an x-ray crystal structure. The anthracene adducts of both E- and Z-l-methyl-1-phenyl-2-neopentyl-2-trimethylsilylsilene undergo a facile, stereospecific decomposition at temperatures as low as 190°C to regenerate their respective silenes, the mildest stereospecific route to a silene yet reported. The E- and Z-silenes react stereospecifically with methanol under vacuum-sealed tube conditions. The stereochemistry of the addition is syn and a common mechanism is proposed for the addition of alcohols and the addition of alkoxysilanes to silenes.
Date: May 1987
Creator: Bates, Tim Frank
Partner: UNT Libraries

Fabrication of high-density cantilever arrays and through-wafer interconnects

Description: Processes to fabricate dense, dry released microstructures with electrical connections on the opposite side of the wafer are described. A 10 x 10 array of silicon and polysilicon cantilevers with high packing density (5 tips/mm<sup>2</sup>) and high uniformity (<10 µm length variation across the wafer) are demonstrated. The cantilever release process uses a deep SF<sub>6</sub>/C<sub>4</sub>F<sub>8</sub>, plasma etch followed by a HBr plasma etch to accurately release cantilevers. A process for fabricating electrical contacts through the backside of the wafer is also described. Electrodeposited resist, conformal CVD metal deposition and deep SF<sub>6</sub>/C<sub>4</sub>F<sub>8</sub> plasma etching are used to make 30 µm/side square vias each of which has a resistance of 50 m(omega).
Date: November 3, 1998
Creator: A. Harley, J.; Abdollahi-Alibeik, S.; Chow, E. M.; Kenney, T. W.; McCarthy, A. M.; McVittie, J. P. et al.
Partner: UNT Libraries Government Documents Department

Test procedures and instructions for single shell tank saltcake cesium removal with crystalline silicotitanate

Description: This document provides specific test procedures and instructions to implement the test plan for the preparation and conduct of a cesium removal test, using Hanford Single Shell Tank Saltcake from tanks 24 t -BY- I 10, 24 1 -U- 108, 24 1 -U- 109, 24 1 -A- I 0 1, and 24 t - S-102, in a bench-scale column. The cesium sorbent to be tested is crystalline siticotitanate. The test plan for which this provides instructions is WHC-SD-RE-TP-024, Hanford Single Shell Tank Saltcake Cesium Removal Test Plan.
Date: January 7, 1997
Creator: Duncan, J.B.
Partner: UNT Libraries Government Documents Department

Solventless sol-gel chemistry through ring-opening polymerization of bridged disilaoxacyclopentanes

Description: Disilaoxacyclopentanes have proven to be excellent precursors to sol-gel type materials. These materials have shown promise as precursors for encapsulation and microelectronics applications. The polymers are highly crosslinked and are structurally similar to traditional sol-gels, but unlike typical sol-gels they are prepared without the use of solvents and water, they have low VOC's and show little shrinkage during processing.
Date: April 4, 2000
Partner: UNT Libraries Government Documents Department

Combining the Best of Bulk and Surface Micromaching Using Si(111) Substrates

Description: This process combines the best features of bulk ad surface micromachining. It enables the production of stress free, thick, virtually arbitrarily shaped structures with well defiti thick or thin sacrificial layers, high sacrificial layer selectivity and large undercuts using IC compatible, processes. The basis of this approach is the use of dy available {111} oriented substrates. anisotropic Si trench etching, S iN masking and KOH etching.
Date: November 30, 1998
Creator: Fleming, J.G.
Partner: UNT Libraries Government Documents Department

Fluorosilicone and silicone o-ring aging study.

Description: Fluorosilicone o-ring aging studies were performed. These studies examined the compressive force loss of fluorosilicone o-rings at accelerated (elevated) temperatures and were then used to make predictions about force loss at room temperature. The results were non-Arrhenius with evidence for a lowering in Arrhenius activation energies as the aging temperature was reduced. The compression set of these fluorosilicone o-rings was found to have a reasonably linear correlation with the force loss. The aging predictions based on using the observed curvature of the Arrhenius aging plots were validated by field aged o-rings that yielded degradation values reasonably close to the predictions. Compression set studies of silicone o-rings from a previous study resulted in good correlation to the force loss predictions for the fluorosilicone o-rings from this study. This resulted in a preliminary conclusion that an approximately linear correlation exists between compression set and force decay values for typical fluorosilicone and silicone materials, and that the two materials age at similar rates at low temperatures. Interestingly, because of the observed curvature of the Arrhenius plots available from longer-term, lower temperature accelerated exposures, both materials had faster force decay curves (and correspondingly faster buildup of compression set) at room temperature than anticipated from typical high-temperature exposures. A brief study on heavily filled conducting silicone o-rings resulted in data that deviated from the linear relationship, implying that a degree of caution must be exercised about any general statement relating force decay and compression set.
Date: October 1, 2007
Creator: Bernstein, Robert & Gillen, Kenneth T.
Partner: UNT Libraries Government Documents Department

Intramolecular condensation reactions of {alpha}, {omega}- bis(triethoxy-silyl)alkanes. Formation of cyclic disilsesquioxanes

Description: Under acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane (1) and 1,4-bis(triethoxysilyl)butane (2) were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed withe the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to perserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.
Date: August 1, 1996
Creator: Loy, D.A.; Carpenter, J.P.; Myers, S.A.; Assink, R.A.; Small, J.H.; Greaves, J. et al.
Partner: UNT Libraries Government Documents Department

Infrared spectroscopy of nonclassical ions and their complexes

Description: This thesis describes an infrared spectroscopic study on the structures and dynamics of the nonclassical ions and their complexes, using ion trap vibrational predissociation spectroscopy. Chapter One provides an introduction to the experimental apparatus used in this work. Chapter Two describes the previous theoretical and experimental works on the carbonium ion CH{sub 5}{sup +} and infrared spectroscopic and theoretical works on CH{sub 5}{sup +}. CH{sub 5}{sup +} was predicted to scramble constantly without possessing a stable structure. In Chapter Three, the infrared spectroscopy for the molecular hydrogen solvated carbonium ions CH{sub 5}{sup +}(H{sub 2}){sub n} (n=1-6) in the frequency region of 2700-4200 cm{sup {minus}1} are presented and compared with the results of ab initio molecular dynamics simulation on CH{sub 5}{sup +}(H{sub 2}){sub n} (n=0-3). The results suggested that the scrambling of CH{sub 5}{sup +} slowed down considerably by the stabilization effects of the solvent H{sub 2} molecules, and it was completely frozen out when the first three H{sub 2} molecules were bound to the core CH{sub 5}{sup +}. Chapter Four presents the complete infrared spectra for the solvated carbonium ions, CH{sub 5}{sup +}(A){sub x}(B){sub y} (A,B=H{sub 2}, Ar, N{sub 2}, CH{sub 4};x,y=0-5) in the frequency region of 2500-3200 cm{sup {minus}1}. As the binding affinities of the solvent molecules and the number of the solvent molecules in the clusters increased, the scrambling of CH{sub 5}{sup +} slowed down substantially. The structures of the solvated carbonium ions and the evidence for rapid proton transfer in CH{sub 5}{sup +}(CH{sub 4}) were also presented. Chapter Five presents the vib-rotational spectrum for the H-H stretching mode of the silanium ion SiH{sub 5}{sup +}. The results suggested that SiH{sub 5}{sup +} can be described as a complex of SiH{sub 3}{sup +} and a freely internally rotating H{sub 2}, analogous to, but distinct from CH{sub 5}{sup +}.
Date: January 1, 1995
Creator: Boo, D.W.
Partner: UNT Libraries Government Documents Department

Results of Scoping Studies for Determining Radiolytic Hydrogen Production from Moist CST and CST Slurries

Description: In support of the Salt Disposition team, scoping studies have been performed on the radiolysis of moist and aqueous slurries of Crystalline Silicotitanate(CST). If CST is used for removal of Cs-137 from SRS salt solutions, radiolysis of the water by Cs-137 on the CST will produce H2. Also it has been shown that the presence of a solid in the system can enhance the production of H2 by transferring absorbed energy from the solid to the water (1). As indicated in the test plan (2) for this scoping study, it is the intent of this study to determine if CST enhances the radiolytic production of H2 and to estimate the radiolytic hydrogen generation rate from an aqueous CST slurry in a column at the maximum expected Cs-137 loading on the CST.Initially several CST slurry systems were irradiated with Co-60 gamma rays and the radiolytic yield of H2 measured in terms of its G value (molecules of H2 produced per 100 eV of energy absorbed). Based on the results of these tests it was determined that CST did not enhance the radiolytic production of H2 by transferring energy to the water and causing it to decompose.Calculations were then performed to estimate the rate of H2 production from a process column 16ft. long by 5ft. in diameter containing CST that was fully loaded with Cs-137. The maximum rate of H2 production based on the G values measured in this study was one liter per minute at STP (0.04 cfm). This was for a 63 percent water/CST slurry with a G value of 0.2 molecules/100eV for H2 production and a loading of 1 gram of Cs-137 per 100 grams of resin. The present work also indicates that for a column containing salt solution and CST rather than water and CST, the rate would ...
Date: December 11, 1998
Creator: Bibler, N.E.
Partner: UNT Libraries Government Documents Department

Mechanisms of strain-induced surface ripple formation and dislocation multiplication in Si{sub x}Ge{sub 1-x} thin films

Description: We discuss the stress driven roughening transition of Si{sub x}Ge{sub 1-x} thin films. In the case of annealed films, nucleation effects dominate the nature of the surface ripple which formed by a cooperative nucleation mechanism. Facetting can however be suppressed at high supersaturations, resulting in a transition with characteristics of the Asaro-Tiller-Grinfeld instability. The relationship between morphological evolution and dislocation nucleation and multiplication is considered.
Date: April 1, 1997
Creator: Jesson, D.E.; Chen, K.M. & Pennycook, S.G.
Partner: UNT Libraries Government Documents Department

Modeling of Crystalline Silicotitanate Ion Exchange Columns

Description: Non-elutable ion exchange is being considered as a potential replacement for the In-Tank Precipitation process for removing cesium from Savannah River Site (SRS) radioactive waste. Crystalline silicotitanate (CST) particles are the reference ion exchange medium for the process. A major factor in the construction cost of this process is the size of the ion exchange column required to meet product specifications for decontaminated waste. To validate SRS column sizing calculations, SRS subcontracted two reknowned experts in this field to perform similar calculations: Professor R. G. Anthony, Department of Chemical Engineering, Texas A&038;M University, and Professor S. W. Wang, Department of Chemical Engineering, Purdue University. The appendices of this document contain reports from the two subcontractors. Definition of the design problem came through several meetings and conference calls between the participants and SRS personnel over the past few months. This document summarizes the problem definition and results from the two reports.
Date: March 9, 1999
Creator: Walker, D.D.
Partner: UNT Libraries Government Documents Department

Test procedures and instructions for Hanford complexant concentrate supernatant cesium removal using CST

Description: This document provides specific test procedures and instructions to implement the test plan for the preparation and conduct of a cesium removal test, using Hanford Complexant Concentrate supernatant liquor from tank 241-AN-107, in a bench-scale column. The cesium sorbent to be tested is crystalline silicotitanate. The test plan for which this provides instructions is WHC-SD-RE-TP-023, Hanford Complexant Concentrate Supernatant Cesium Removal Test Plan.
Date: January 8, 1997
Creator: Hendrickson, D.W.
Partner: UNT Libraries Government Documents Department

Bridged polysilsesquioxanes: A molecular based approach for the synthesis of functional hybrid materials

Description: Bridged polysilsesquioxanes (BPS) are a family of hybrid organic-inorganic materials prepared by sol-gel polymerization of molecular building blocks that contain a variable organic component and at least two trifunctional silyl groups. The resulting xerogels and aerogels have physical and mechanical properties that are strongly influenced by the organic bridging group. This talk focuses on the synthesis of functional bridged polysilsesquioxanes. Incorporation of functional groups that respond to chemical, photochemical, or thermal stimuli can provide handles for modifying bulk morphology and/or provide function. These materials can find use as ion exchange media, chromatographic stationary phases, photoresists and high capacity selective chemical absorbents.
Date: May 9, 2000
Partner: UNT Libraries Government Documents Department

Hanford tank waste supernatant cesium removal test plan

Description: This document provides the test plan for the preparation and conduct of a cesium removal test using Hanford DSSF supernatant liquor from tank 241-AW-101 in a bench-scale column. Cesium sorbents to be tested include resorcinol-formaldehyde resin and crystalline silicotitanate.
Date: May 31, 1996
Creator: Hendrickson, D.W., Westinghouse Hanford
Partner: UNT Libraries Government Documents Department

Polysilsesquioxanes through base-catalyzed redistribution of oligohydridosiloxanes

Description: Organopolysilsesquioxanes have recently gained much interest as materials for low-K dielectrics, ceramic precursors and photoresists. Typical sol-gel synthesis of polysilsesquioxanes involves the hydrolysis of organotricholorosilanes and/or organotrialkoxysilanes in the presence of acid or base catalysts and organic solvents. However, under sol-gel conditions most organotrialkoxysilanes do not afford silsesquioxane gels. This limits the range of organic functionalities that can be introduced into these hybrid organic-inorganic materials. An alternative route to polysilsesquioxanes is through oligohydridosiloxanes. Catalytic disproportionation, by titanium complexes, of linear or cyclic oligomers of methylhydridosiloxanes can lead to polymethylsilsesquioxanes. The authors have shown that disproportionation of oligomethylhydridosiloxanes can also be catalyzed by tetrabutylammonium hydroxide to yield polymethylsilsesquioxanes (scheme 1). This replaces the step-growth sol-gel polymerization process of organotrialkoxysilanes, which requires solvent, stoichiometric water and produces alcohol and water condensation by-products. Tetraalkylammonium hydroxides, as catalysts, are also attractive because they readily decompose by heating above 150 C; thus, they can be easily removed from the final materials. In this paper the authors report on both the catalytic and stoichiometric redistribution of organohydridosiloxanes to produce polysilsesquioxane foams and gels of the formula (RSiO{sub 1.5}){sub n} which otherwise cannot be obtained through traditional sol-gel means.
Date: May 1, 2000
Partner: UNT Libraries Government Documents Department

Porosity in polysilsesquioxane xerogels

Description: Polysilsesquioxanes, [RSiO{sub 1.5}]{sub n} are a class of hybrid organic-inorganic materials in which silicon atoms are linked with up to three siloxane bonds to other monomer units in the polymer and the organic group is a pendent functionality. Polysilsesquioxanes are prepared by the hydrolysis and condensation of organotrialkoxysilanes (Scheme l). Organotrialkoxysilanes RSi(OR{prime}){sub 3}, have been extensively used as coupling agents for composites or surface treatments for materials. Polysilsesquioxanes have become increasingly popular for generating specialty coatings such as low k dielectric materials for microelectronic applications. While there is extensive information on the formation of polysilsesquioxanes, there has not been a survey of the ability of organotrialkoxysilanes to form gels until recently. The formation of polysilsesquioxanes gels has been shown to be very sensitive to the nature of the organic group. Many monomers will only form soluble oligomers or polymers upon hydrolysis and condensation, even when the reaction is conducted solvent-free with neat monomer and aqueous catalyst. Furthermore, there is little information concerning the influence of the organic group, R, on the porosity of the polysilsesquioxanes gels that are formed. In this paper the authors describe the preparation of polysilsesquioxane gels where R = H, methyl, ethyl, cyanoethyl, vinyl, dodecyl, hexadecyl, octadecyl, chloromethyl, and chloromethylphenyl, and the characterization of the porosity of the respective xerogels. Gels were prepared from the hydrolysis and condensation of organotrimethoxysilanes, RSi(OEt){sub 3}, and organotriethoxy-silanes, RSi(OEt){sub 3}.
Date: May 9, 2000
Partner: UNT Libraries Government Documents Department

Sol-gel chemistry by ring-opening polymerization

Description: Sol-gel processing of materials is plagued by shrinkage during polymerization of the alkoxide monomers and processing (aging and drying) of the resulting gels. The authors have developed a new class of hybrid organic-inorganic materials based on the solventless ring-opening polymerization (ROP) of monomers bearing the 2,2,5,5-tetramethyl-2,5-disilaoxacyclopentyl group, which permits them to drastically reduce shrinkage in sol-gel processed materials. Because the monomers are polymerized through a chain growth mechanism catalyzed by base rather than the step growth mechanism normally used in sol-gel systems, hydrolysis and condensation products are entirely eliminated. Furthermore, since water is not required for hydrolysis, an alcohol solvent is not necessary. Monomers with two disilaoxacyclopentyl groups, separated by a rigid phenylene group or a more flexible alkylene group, were prepared through disilylation of the corresponding diacetylenes, followed by ring closure and hydrogenation. Anionic polymerization of these materials, either neat or with 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane as a copolymer, affords thermally stable transparent gels with no visible shrinkage. These materials provide an easy route to the introduction of sol-gel type materials in encapsulation of microelectronics, which they have successfully demonstrated.
Date: February 7, 2000
Creator: Rahimian, Kamyar & Loy, Douglas A.
Partner: UNT Libraries Government Documents Department

Multilayer coating and tests of a 10x extreme ultraviolet lithographc camera

Description: A new set of mirrors for the SANDIA I OX microstepper has been fabricated. The optics have been tested by optical profilometry, atomic force microscopy, EUV reflectometry and EUV scattering. These measurements allow one to predict the performance of the camera. Mo/Si multilayer coatings with the required thickness profile were produced by DC magnetron sputtering using shadow masks in front of the rotating substrates. The failure errors of the new mirrors (0.6 nm) are considerably smaller than those obtained previously, while mid-spatial frequency roughness still needs improvement. This roughness reduces mostly the throughput of the system; i. e. most of the scattered light occurs outside the field of the camera and there is only a small reduction of contrast or resolution.
Date: February 19, 1998
Creator: Spiller, E.; Weber, F. J.; Montcalm, C.; Baker, S. L.; Gullikson, E. M. & Underwood, J. H.
Partner: UNT Libraries Government Documents Department

Evaporation-Induced Self-Assembly of Hybrid Bridged Silsesquioxane Film and Particulate Mesophases with Integral Organic Functionality

Description: Since the discovery of surfactant-templated silica mesophases, the development of organic modification schemes to impart functionality to the pore surfaces has received much attention. Most recently, using the general class of compounds referred to as bridged silsesquioxanes (RO){sub 3}Si-R{prime}-Si(OR){sub 3} (Scheme 1), three research groups have reported the formation of a new class of poly(bridgedsilsesquioxane) mesophases BSQMs with integral organic functionality. In contrast to previous hybrid mesophases where organic ligands or molecules are situated on pore surfaces, this class of materials necessarily incorporates the organic constituents into the framework as molecularly dispersed bridging ligands. Although it is anticipated that this new mesostructural organization should result in synergistic properties derived from the molecular scale mixing of the inorganic and organic components, few properties of BSQMs have been measured. In addition samples prepared to date have been in the form of granular precipitates, precluding their use in applications like membranes, fluidics, and low k dielectric films needed for all foreseeable future generations of microelectronics.
Date: June 12, 2000
Partner: UNT Libraries Government Documents Department

A Mechanistic Investigation of Gelation. The Sol-Gel Polymerization of Bridged Silsesquioxane Monomers

Description: The study of a homologous series of silsesquioxane monomers has uncovered striking discontinuities in gelation behavior. An investigation of the chemistry during the early stages of the polymerization has provided a molecular basis for these observations. Monomers containing from one to four carbon atoms exhibit a pronounced tendency to undergo inter or intramolecular cyclization. The cyclic intermediates have been characterized by {sup 29}Si NMR, chemical ionization mass spectrometry and isolation from the reaction solution. These carbosiloxanes are local thermodynamic sinks that produce kinetic bottlenecks in the production of high molecular weight silsesquioxanes. The formation of cyclics results in slowing down or in some cases completely shutting down gelation. An additional finding is that the cyclic structures are incorporated intact into the final xerogel. Since cyclization alters the structure of the building block that eventually makes up the xerogel network, it is expected that this will contribute importantly to the bulk properties of the xerogel as well.
Date: July 14, 2000
Partner: UNT Libraries Government Documents Department

High Temperature Alkali Corrosion of Dense SN4 Coated with CMZP and Mg-Doped A21TiO5 in Coal Gas

Description: Over the past twenty years silicon based ceramics have generated considerable enthusiasm in the scientific community. Of particular interest is Si3N4, one of the leading candidates of this family, for very demanding structural applications. Its properties are well known and include a high strength to weight ratio, a high chemical resistance, and excellent high temperature properties. However, it was reported in previous papers that the performances of Si3N4 were dramatically affected by hot alkali molten salts. In order to alleviate this phenomenon, it was suggested that certain oxide ceramics, which exhibit better resistance to the alkali corrosion, could be applied as protective coatings. Using the sol-gel process and dip coating technique, CMZP and Mg-doped Al2TiO5 thin films were deposited on Si3N4 substrates and exposure to a sodium containing atmosphere was carried out. During this reporting period, the emphasis was placed on investigating the microstrutural changes of coated and uncoated samples as well as on assessing their alkali corrosion resistance.
Date: March 1, 1998
Creator: Brown, J. J. & Thierry, Nguyen
Partner: UNT Libraries Government Documents Department

Bridged polysilsesquioxane xerogels: A molecular based approach for the preparation of porous hybrid organic-inorganic materials

Description: Bridged polysilsesquioxanes represent an interesting family of hybrid organic-inorganic composite materials. It has been shown that manipulation of the organic bridging component offers the potential for the synthesis of a variety of materials with a range of surface areas and porosities. In addition, incorporation of a heteroatom within the bridging organic component allows for further chemical transformation of the polysilsesquioxane material.
Date: June 1, 1995
Creator: Small, J.H.; Shea, K.J. & Loy, D.A.
Partner: UNT Libraries Government Documents Department

Structure-function relationships of second hyperpolarizabilities in two-dimensional molecules

Description: The enhancement of the third order susceptibilities X{sup (3)} and second order molecular hyperpolarizabilities <{gamma}> in a series of covalently stacked dimer and trimer macrocycles (SiPc and SiNc) was observed through the phase conjugated signals from DFWM measurements at both 1064 and 532 nm. The FWHM of the phase conjugated signals at 532 nm is much smaller than those at 1064 nm and those of the reference compound CS{sub 2}. The <{gamma}> values at both wavelengths as a function of number of the monomer units (n) have an approximate n{sup 3} dependence, differing only in the scaling constant. The origin of such enhancement is discussed and compared to those in one-dimensional {pi}-conjugated systems.
Date: July 1, 1995
Creator: Chen, L.X.; Mandal, B.K. & Bihari, B.
Partner: UNT Libraries Government Documents Department