Making use of polypropylene samples that are selectively labeled with carbon-13 at each of the three unique positions within the repeating unit, we are conducting mass spectral analyses of the volatile organic oxidation products that are produced when the polymer is subjected to elevated temperature in the presence of air. By examination of both the parent and fragmentation ion peaks in the mass spectrum, we are able to identify the positioning of the C-13 labels within the volatile compounds, and thereby map each compound onto its site of origin from within the macromolecular structure of polypropylene. Most of the organic oxidation products are remarkably specific in terms of their genesis from the polymer. The structural results are discussed in terms of the oxidation chemistry of the macromolecule.
This report summarizes results generated on a 5-year cable-aging program that constituted part of the Nuclear Energy Plant Optimization (NEPO) program, an effort cosponsored by the U. S. Department of Energy (DOE) and the Electric Power Research Institute (EPRI). The NEPO cable-aging effort concentrated on two important issues involving the development of better lifetime prediction methods as well as the development and testing of novel cable condition-monitoring (CM) techniques. To address improved life prediction methods, we first describe the use of time-temperature superposition principles, indicating how this approach improves the testing of the Arrhenius model by utilizing all of the experimentally generated data instead of a few selected and processed data points. Although reasonable superposition is often found, we show several cases where non-superposition is evident, a situation that violates the constant acceleration assumption normally used in accelerated aging studies. Long-term aging results over extended temperature ranges allow us to show that curvature in Arrhenius plots for elongation is a common occurrence. In all cases the curvature results in a lowering of the Arrhenius activation energy at lower temperatures implying that typical extrapolation of high temperature results over-estimates material lifetimes. The long-term results also allow us to test the significance of extrapolating through the crystalline melting point of semi-crystalline materials. By utilizing ultrasensitive oxygen consumption (UOC) measurements, we show that it is possible to probe the low temperature extrapolation region normally inaccessible to conventional accelerated aging studies. This allows the quantitative testing of the often-used Arrhenius extrapolation assumption. Such testing indicates that many materials again show evidence of ''downward'' curvature (E{sub a} values drop as the aging temperature is lowered) consistent with the limited elongation results and many literature results. It is also shown how the UOC approach allows the probing of temperatures that cross through the crystalline melting point region of semi-crystalline materials such as XLPO and EPR cable insulations. New results on combined environment aging of neoprene and hypalon cable jacketing materials are presented and offer additional evidence in support of our time-temperature-dose rate (t-T-DR) superposition approach that had been used successfully in the past for such situations.
Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes as adaptive or smart materials. Dimensional adjustments of adaptive polymer films depend on controlled charge deposition. Predicting their long-term performance requires a detailed understanding of the piezoelectric material features, expected to suffer due to space environmental degradation. Hence, the degradation and performance of PVDF and its copolymers under various stress environments expected in low Earth orbit has been reviewed and investigated. Various experiments were conducted to expose these polymers to elevated temperature, vacuum UV, {gamma}-radiation and atomic oxygen. The resulting degradative processes were evaluated. The overall materials performance is governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure is evident as depoling, loss of orientation and surface erosion. The effects of combined vacuum UV radiation and atomic oxygen resulted in expected surface erosion and pitting rates that determine the lifetime of thin films. Interestingly, the piezo responsiveness in the underlying bulk material remained largely unchanged. This study has delivered a comprehensive framework for material properties and degradation sensitivities with variations in individual polymer performances clearly apparent. The results provide guidance for material selection, qualification, optimization strategies, feedback for manufacturing and processing, or alternative materials. Further material qualification should be conducted via experiments under actual space conditions.
Smart polymeric materials, such as piezoelectric polymers which deform by application of an electric field, are of interest for use in controllable mirrors as large, lightweight space optics. An important consideration when using any organic material in a space application is their extreme vulnerability to the space environment. In LEO the presence of atomic oxygen, large thermal extremes, hard vacuum, short wavelength ultraviolet and particulate radiation can result in erosion, cracking and outgassing of most polymers. While much research has been performed examining the physical and chemical changes incurred by polymers exposed to actual and simulated LEO environments, little work has focused on the effects of the space environment on the performance of piezoelectric polymers. The most widely used piezoelectric polymers are those based on poly(vinylidene fluoride) (PVDF) and include copolymers synthesized from vinylidene fluoride and trifluoroethylene, hexafluoropropylene or chlorotrifluoroethylene. The presence of a comonomer group can greatly influence on the crystalline phase, melting point, Curie point, modulus and processing required for piezoelectricity. After a rigorous pre-selection process only two polymers, namely the PVDF homopolymer and a TrFE copolymer (80% comonomer content), satisfied most of the requirements for operation in the temperature/radiation environment of LEO. Based on this initial materials selection, we have now performed a detailed study of the effects of temperature, atomic oxygen and vacuum UV radiation simulating low Earth orbit conditions on these two polymers. Both polymers exhibited diminished but very stable piezoelectric performance up to 130 C despite the upper use temperatures suggested by industry of 80 C (PVDF) and 100 C (P(VDF-TrFE)). We believe that the loss of piezoelectric response in samples conditioned at 130 C compared with non-exposed samples is partly due to the depoling process which occurs when the highly stressed films undergo contraction via relaxation. The TrFE copolymer, which does not need to be stretched for the polar phase to be present, has better retention of piezoelectric properties at 130 C compared with the highly oriented homopolymer. AO/VUV exposure caused significant surface erosion and pattern development for both polymers. Erosion yields were 2.8 x 10{sup -24} cm{sup 3}/atom for PVDF and 2.5 x 10{sup -24} cm{sup 3}/atom for P(VDF-TrFE). The piezoelectric properties of the residual material for both polymers were largely unchanged after exposure, although a slight shift in the Curie transition of the P(VDF-TrFE) was observed. A lightly crosslinked network was formed in the copolymer, presumably due to penetrating VUV radiation, while the homopolymer remained uncrosslinked. These differences were attributed to different levels of crystallinity and increased VUV absorption by P(VDF-TrFE) over PVDF. In this paper a summary of the performance limiting effects of temperature, radiation, atomic oxygen and VUV on the piezoelectric response of PVDF based polymers will be presented.
Smart polymeric materials, such as piezoelectric polymers which deform by application of an electric field, are of interest for use in controllable mirrors as large, lightweight space optics. An important consideration when using any organic material in a space application is their extreme vulnerability to the space environment. In LEO the presence of atomic oxygen, large thermal extremes, hard vacuum, short wavelength ultraviolet and particulate radiation can result in erosion, cracking and outgassing of most polymers. While much research has been performed examining the physical and chemical changes incurred by polymers exposed to actual and simulated LEO environments, little work has focused on the effects of the space environment on the performance of piezoelectric polymers. The most widely used piezoelectric polymers are those based on poly(vinylidene fluoride) (PVDF) and include copolymers synthesized from vinylidene fluoride and trifluoroethylene, hexafluoropropylene or chlorotrifluoroethylene. The presence of a comonomer group can greatly influence on the crystalline phase, melting point, Curie point, modulus and processing required for piezoelectricity. After a rigorous pre-selection process only two polymers, namely the PVDF homopolymer and a TrFE copolymer (80% comonomer content), satisfied most of the requirements for operation in the temperature/radiation environment of LEO. Based on this initial materials selection, we have now performed a detailed study of the effects of temperature, atomic oxygen and vacuum UV radiation simulating low Earth orbit conditions on these two polymers. Both polymers exhibited diminished but very stable piezoelectric performance up to 130 C despite the upper use temperatures suggested by industry of 80 C (PVDF) and 100 C (P(VDF-TrFE)). We believe that the loss of piezoelectric response in samples conditioned at 130 C compared with non-exposed samples is partly due to the depoling process which occurs when the highly stressed films undergo contraction via relaxation. The TrFE copolymer, which does not need to be stretched for the polar phase to be present, has better retention of piezoelectric properties at 130 C compared with the highly oriented homopolymer. AO/VUV exposure caused significant surface erosion and pattern development for both polymers. Erosion yields were 2.8 x 10{sup -24} cm{sup 3}/atom for PVDF and 2.5 x 10{sup -24} cm{sup 3}/atom for P(VDF-TrFE). The piezoelectric properties of the residual material for both polymers were largely unchanged after exposure, although a slight shift in the Curie transition of the P(VDF-TrFE) was observed. A lightly crosslinked network was formed in the copolymer, presumably due to penetrating VUV radiation, while the homopolymer remained uncrosslinked. These differences were attributed to different levels of crystallinity and increased VUV absorption by P(VDF-TrFE) over PVDF. In this paper a summary of the performance limiting effects of temperature, radiation, atomic oxygen and VUV on the piezoelectric response of PVDF based polymers will be presented.
An S-band 20 MeV electron linear accelerator formerly used for medical applications has been recommissioned to provide a wide range of photonuclear activation studies as well as various radiation effects on biological and microelectronic systems. Four radiation effect applications involving the electron/photon beams are described. Photonuclear activation of a stable isotope of oxygen provides an active means of characterizing polymer degradation. Biological irradiations of microorganisms including bacteria were used to study total dose and dose-rate effects on survivability and the adaptation of these organisms to repeated exposures. Microelectronic devices including bipolar junction transistors (BJTs) and diodes were irradiated to study photocurrent from these devices as a function of peak dose rate with comparisons to computer modeling results. In addition, the 20 MeV linac may easily be converted to a medium energy neutron source which has been used to study neutron damage effects on transistors.
Solid-state {sup 1}H NMR relaxometry studies were conducted on a hydroxy-terminated polybutadiene (HTPB) based polyurethane elastomer thermo-oxidatively aged at 80 C. The {sup 1}H T{sub 1}, T{sub 2}, and T{sub 1{rho}} relaxation times of samples thermally aged for various periods of time were determined as a function of NMR measurement temperature. The response of each measurement was calculated from a best-fit linear function of the relaxation time vs. aging time. It was found that the T{sub 2,H} and T{sub 1{rho},H} relaxation times exhibited the largest response to thermal degradation, whereas T{sub 1,H} showed minimal change. All of the NMR relaxation measurements on solid samples showed significantly less sensitivity to thermal aging than the T{sub 2,H} relaxation times of solvent-swollen samples.
Thin polymer films have been identified as one of the major enabling technologies for future space-based systems. Potential devices include those based on piezoelectric bimorph polymers that deform when a charge is deposited, for example, from an electron gun. The thin-film and lightweight nature of the polymeric devices will allow them to be launched more readily and deployed to operating conditions once in orbit. Until now little work has been done aimed at investigating the performance of piezoelectric properties of PVDF and its copolymers and the prediction of their long-term stability in low Earth orbit (LEO) environmental conditions. In this paper, the piezoelectric properties of PVDF and the copolymers formed from polymerization of vinylidene fluoride and trifluoroethylene (TrFE) or hexafluoropropylene (HFP) have been studied over a broad temperature range simulating that expected in LEO. The temperatures experienced by unprotected polymers on low altitude spacecraft have previously been reported as ranging from approximately -100 C to +130 C as the polymer/spacecraft passes in and out of the Earth's shadow. To examine the effects of temperature on the piezoelectric properties of poled PVDF, P(VDF-TrFE) and P(VDF-HFP) the d{sub 33} piezoelectric coefficients and electric displacement-electric field (D-E) hysteresis loops were measured up to 160 C for the d{sub 33} measurements and from -80 to +110 C for the D-E loops. The room temperature d{sub 33} coefficient of PVDF homopolymer films, annealed for extended periods at 50, 80 and 125 C, dropped rapidly within a few days of heating, then remained unchanged for periods of up to 300 days. In contrast, the TrFE copolymer exhibited greater thermal stability than the homopolymer, with the d{sub 33} remaining almost unchanged from the pre-annealing value after heating at 50, 80 and 125 C. The HFP copolymer exhibited poor retention of d33 at temperatures above 80 C. For all three polymers short term annealing at 160 C reduced the d{sub 33} to zero. The decrease in d{sub 33} for the TrFE copolymer was correlated with the change in Curie temperature upon annealing of the copolymer, as observed by differential scanning calorimetry (DSC). Unlike radiation damage, which may occur from vacuum UV and atomic oxygen in LEO, the depoling of the polymers on exposure to elevated temperatures was attributed to a physical randomization of the morphology rather than a chemical degradation process. In situ D-E loop measurements over the temperature range -80 to +110 C showed that the remnant polarization of the TrFE copolymer was more stable than the PVDF homopolymer. These results suggest that the TrFE copolymer appears to have a better overall performance in thermal extremes compared with PVDF or an HFP copolymer.
The effect of the density and in-plane distribution of interfacial interactions on crack initiation in an epoxy-silicon joint was studied in nominally pure shear loading. Well-defined combinations of strong (specific) and weak (nonspecific) interactions were created using self-assembling monolayers. The in-plane distribution of strong and weak interactions was varied by employing two deposition methods: depositing mixtures of molecules with different terminal groups resulting in a nominally random distribution, and depositing methyl-terminated molecules in domains defined lithographically with the remaining area interacting through strong acid-base interactions. The two distributions lead to very different fracture behavior. For the case of the methyl-terminated domains (50 {micro}m on a side) fabricated lithographically, the joint shear strength varies almost linearly with the area fraction of strongly interacting sites. From this we infer that cracks nucleate on or near the interface over nearly the entire range of bonded area fraction and do so at nearly the same value of local stress (load/bonded area). We postulate that the imposed heterogeneity in interfacial interactions results in heterogeneous stress and strain fields within the epoxy in close proximity to the interface. Simply, the bonded areas carry load while the methyl terminated domains carry negligible load. Stress is amplified adjacent to the well-bonded regions (and reduced adjacent to the poorly bonded regions), and this leads to crack initiation by plastic deformation and chain scission within the epoxy near the interface. For the case of mixed monolayers, the dependence is entirely different. At low areal density of strongly interacting sites, the joint shear strength is below the detection limit of our transducer for a significant range of mixed monolayer composition. With increasing density of strongly interacting sites, a sharp increase in joint shear strength occurs at a methyl terminated area fraction of roughly 0.90. We postulate that this coincides with the onset of yielding in the epoxy. For methyl-terminated area fractions less than 0.85, the joint shear strength becomes independent of the interfacial interactions. This indicates that fracture no longer initiates on the interface but away from the interface by a competing mechanism, likely plastic deformation and chain scission within the bulk epoxy. The data demonstrate that the in-plane distribution of interaction sites alone can affect the location of crack nucleation and the far-field stress required.
A hydroxy-terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) elastomer is commonly used as propellant binder material. The thermal degradation of the binder is believed to be an important parameter governing the performance of the propellant. The aging of these binders can be monitored by mechanical property measurements such as modulus or tensile elongation. These techniques, however, are not easily adapted to binder agents that are dispersed throughout a propellant. In this paper the authors investigated solid state NMR relaxation times as a means to predict the mechanical properties of the binder as a function of aging time. {sup 1}H spin-lattice and spin-spin relaxation times were found to be insensitive to the degree of thermal degradation of the elastomer. Apparently these relaxation times depend on localized motions that are only weakly correlated with mechanical properties. A strong correlation was found between the {sup 13}C cross-polarization (CP) NMR time constant, T{sub cp}, and the tensile elongation at break of the elastomer as a function of aging time. A ramped-amplitude CP experiment was shown to be less sensitive to imperfections in setting critical instrumental parameters for this mobile material.
The authors have shown that the hydroperoxide species in {gamma}-irradiated {sup 13}C-polyethylene can be directly observed by {sup 13}C MAS NMR spectroscopy. The experiment was performed without the need for special sample preparation such as chemical derivatization or dissolution. Annealing experiments were employed to study the thermal decomposition of the hydroperoxide species and to measure an activation energy of 98 kJ/mol. EPR spectroscopy suggests that residual polyenyl and alkylperoxy radicals are predominantly trapped in interracial or crystalline regions, while the peroxy radicals observed after UV-photolysis of hydroperoxides are in amorphous regions.
We report an evaporation-induced self-assembly procedure to prepare poly(bridged silsesquioxane) thin-film and particulate mesophases that incorporate organic moieties (1-3) into periodic, mesostructured frameworks as molecularly dispersed bridging ligands. Capacitance-voltage measurements along with a variety of structural characterization procedures were performed to begin to elucidate structure-property relationships of this new class of surfactant-templated mesophases. We observed a consistent trend of increasing modulus and hardness and decreasing dielectric constant with substitution of the bridged silsesquioxane (≡Si-(CH2)2-Si≡) for siloxane (≡Si-O-Si≡) in the framework. This preliminary evidence suggests that the introduction of integral organic groups into the frameworks of mesoporous materials can result in synergistic properties, promising an unprecedented ability to tune properties and function.
Self-assembled monolayers (SAMS) are commonly produced by immersing substrates in organic solutions containing trichlorosilane coupling agents. Unfortunately, such deposition solutions can also form alternate structures including inverse micelles and lamellar phases. The formation of alternate phases is one reason for the sensitivity of SAM depositions to factors such as the water content of the deposition solvent. If such phases are present, the performance of thin films used for applications such as minimization of friction and stiction in micromachines can be seriously compromised. Inverse micelle formation has been studied in detail for depositions involve 1H-, 1H-, 2H-, 2H-perfluorodecyltrichlorosilane (FDTS) in isooctane. Nuclear magnetic resonance experiments have been used to monitor the kinetics of hydrolysis and condensation reactions between water and FDTS. Light scattering experiments show that when hydrolyzed FDTS concentrations reach a critical concentration, there is a burst of nucleation to form high concentrations of spherical agglomerates. Atomic force microscopy results show that the agglomerates then deposit on substrate surfaces. Deposition conditions leading to monolayer formation involve using deposition times that are short relative to the induction time for agglomeration. After deposition, inverse micelles can be converted into lamellar or monolayer structures with appropriate heat treatments if surface concentrations are relatively low.
The {gamma}-irradiated-oxidation of pentacontane (C{sub 50}H{sub 102}) and the polymer polyisoprene was investigated as a function of oxidation level using {sup 17}O nuclear magnetic resonance (NMR) spectroscopy. It is demonstrated that by using {sup 17}O labeled O{sub 2} gas during the {gamma}-irradiation process, details about the oxidative degradation mechanisms can be directly obtained from the analysis of the {sup 17}O NMR spectra. Production of carboxylic acids is the primary oxygen-containing functionality during the oxidation of pentacontane, while ethers and alcohols are the dominant oxidation product observed for polyisoprene. The formation of ester species during the oxidation process is very minor for both materials, with water also being produced in significant amounts during the radiolytic oxidation of polyisoprene. The ability to focus on the oxidative component of the degradation process using {sup 17}O NMR spectroscopy demonstrates the selectivity of this technique over more conventional approaches.
Oligomethylhydridosiloxane and tis copolymer with dimethylsiloxane undergo redistribution chemistry with catalytic tetrabutylammonium hydroxide (TBAH) to produce methylsilane and polymethylsilsesquioxanes. The rate and extent of redistribution reaction can be controlled by the amount of TBAH added, as well as use of solvent. The extent reaction can be followed by both infrared radiation (IR) and solid state NMR spectroscopy, following the disappearance of the SiH in the starting oligosiloxane.
Polysilsesquioxane foams and gels of the formula (RSiO1.5)n were produced via the catalytic an stoichiometric redistribution of organohydridosiloxanes. The extent of reaction was followed by both infrared (IR) and solid state NMR spectroscopy, following the disappearance of the SiH in the starting oligosiloxane.
{sup 13}C-enriched polyethylene was subjected to {gamma}-irradiation in the presence of air at 25 and 80 C for total doses ranging from 71 to 355 kGy. Significant quantities of hydroperoxides were detected in the 25 C irradiated sample by {sup 13}C magic angle spinning NMR spectroscopy. This method of detection was performed on the solid polymer and required no chemical derivatization or addition of solvent. The chemical stability and subsequent products of the hydroperoxide species were studied by annealing the irradiated samples in air at temperatures ranging from 22 to 110 C. A time-temperature superposition analysis provided an activation energy of 108 kJ/mol for the hydroperoxide decomposition process. The primary products of hydroperoxide decomposition were ketones and secondary alcohols with lesser amounts of acids and esters. EPR measurements suggest that the reactive hydroperoxide species reside in the amorphous phase of polyethylene, consistent with degradation occurring in the amorphous phase.
The precise pore sizes defined by crystalline zeolite lattices have led to intensive research on zeolite membranes. Unfortunately zeolites have proven to be extremely difficult to prepare in a defect-free thin film form needed for membrane flux and selectivity. We introduce tetrapropylammonium (TPA), a structure-directing agent for zeolite ZSM-5, into a silica sol and exploit the development of high solvation stresses to create templated amorphous silicas with pore apertures comparable in size to those of ZSM-5. Silicon and carbon NMR experiments were performed to evaluate the efficacy of our templating approach. The {sup 29}Si NMR spectrum of the silica matrix was observed by an intermolecular cross-polarization experiment involving the {sup 1}H nuclei of TPA and the {sup 29}Si nuclei in the silica matrix. The efficiency of the cross-polarization interaction was used to investigate the degree to which the matrix formed a tight cage surrounding the template molecule. Bulk xerogels, prepared by gelation and slow drying of the corresponding sols, exhibited only weak interactions between the two sets of nuclei. Thin film xerogels, where drying stresses are greater, exhibited significantly increased interactions. Intramolecular cross-polarization experiments between the {sup 1}H and {sup 13}C nuclei of the template molecule demonstrated that much of the increased efficiency was a result of reduced rotational mobility of the TPA molecule.
Long range substituent effects on the 29Si NMR chemical shifts in a series of alkylene and arylene-bridged triethoxysilanes were observed over as many as 11 bonds. The hydrolysis reaction of an ethoxide caused the resonance of the silicon on the opposing end of the bridging unit to move downfield. The alkylene bridging units ranged from ethylene to octylene while the arylene bridging units included phenyl and biphenyl. Resonance assignments were confirmed by the absence of these shifts for the triethoxysilyl in l-triphenylsilyl-2-triethoxysilylethane. The magnitude of the downfield shift decreased as the length of the bridging unit between silicon atoms increased. Transmission of the substituent effect along a polyethylene chain was successfully modeled by a through-bond mechanism with an attenuation factor of 1.88 for each methylene unit.
The porosities of three mesoporous silica materials were characterized with {sup 129}Xe NMR spectroscopy. The materials were synthesized by a sol-gel process with r = 0, 25, and 70% methanol by weight in an aqueous cetyltrimethylammonium bromide solution. Temperature dependent chemical shifts and spin lattice relaxation times reveal that xenon does not penetrate the pores of the largely disordered (r= 70%) silica. For both r = 0 and 25%, temperature dependent resonances corresponding to physisorbed xenon were observed. An additional resonance for the r = 25% sample was attributed to xenon between the disordered cylindrical pores. 2D NMR exchange experiments corroborate the spin lattice relaxation data which show that xenon is in rapid exchange between the adsorbed and the gas phase.
A fundamental understanding of aging in an organic material requires that one understand how aging affects the chemical structure of a material, and how these chemical changes are related to the material`s macroscopic properties. This level of understanding is usually achieved by examining the material on a variety of length scales ranging from atomic to meso-scale to macroscopic. The authors are developing and applying several {sup 13}C nuclear magnetic resonance (NMR) spectroscopy experiments to characterize the aging process of organic materials over a broad range of length scales. Examples of studies which range from atomic to macroscopic will be presented.
The hydrolysis and self- and cross-condensation kinetics of the hybrid sol tetraethoxysilane and ethyltriethoxysilane were investigated by high resolution {sup 29}Si NMR spectroscopy. A kinetic model in which hydrolysis is reversible and condensation is irreversible was developed. The authors found excellent agreement between the product distributions measured by {sup 29}Si NMR spectroscopy and calculated by the model. The cross-condensation rates for each of the sols were intermediate to the condensation rates of the individual components. Calculations show that for these sols, the concentration of cross-condensed species is a weak function of the relative rates of self-condensation.
Structure and properties of a series of modified polydimethylsiloxane (PDMS) elastomers reinforced by {ital in situ} generated silic particles were investigated. The PDMS elastomer was modified by systematically varying the molecular weight between reactive groups incorporated into the backbone. Tetraethoxysilane (TEOS) and partial hydrolyzate of TEOS were used to generate silic particles. Chemistry and phase structure of the materials were investigated by {sup 29}Si magic angle spinning nuclear magnetic resonance spectroscopy and swelling experiments.
The chemical synthesis of advanced ceramic and glass materials by the sol-gel process has become an area of increasing activity in the field of material science. The sol-gel process provides a means to prepare homogeneous, high purity materials with tailored chemical and physical properties. This paper surveyed the nuclear magnetic resonance (NMR) studies of silicon-based sol-gel kinetics. A review of the various models which have been used to analyze the chemical kinetics of various sol-gel systems was presented. The utility of NMR spectroscopy was demonstrated in investigating the influence that various reaction conditions have on the reaction pathways by which sol-gel derived materials are synthesized. By observing in a direct fashion the chemical pathway of the sol-gel, it is often possible to relate the final properties of the material to the formulation and reaction conditions of the sol-gel. The study of reaction kinetics by NMR is expected to play an increasingly important role in understanding sol-gel processing and material properties. 15 refs. (DP)
This paper surveys a few of the current issues in sol-gel reaction kinetics. Many times seemingly modest changes in reactants or reaction conditions can lead to substantial differences in the overall reaction rates and pathways. For example, qualitative features of the reaction kinetics can depend on catalyst concentration. At very high acid-catalyst concentrations, reverse are significant for TMOS sol-gels, while for moderate acid-catalyst concentrations, reverse reactions are substantially reduced. The reaction kinetics are substantially reduced. The reaction kinetics of two similar tetraalkoxysilanes: tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS), can be markedly different under identical reaction conditions. Under acid-catalyzed reaction conditions, a TMOS sol-gel undergoes both water-and alcohol-producing condensation reactions while a TEOS sol-gel undergoes only water-producing condensation. The early time hydrolysis and condensation reactions of a TMOS sol-gel are statistical in nature and can be quantitatively described by a few simple reaction rate constants while the reaction behavior of a TEOS sol-gel is markedly nonstatistical. A comprehensive theory of sol-gel kinetics must address diverse experimental findings. 9 refs., 3 figs., 1 tab.
