Search NASA⌕ Search

SEARCH · Search NASA

Results for “polycondensation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

68 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

Polyarylene Ethers with Improved Properties

This invention relates to novel polyarylene ethers which possess the combination of high strength, toughness, and high use temperature with ease of extrusion and formation into complex objects. These polyarylene ethers are suitable for use in adhesives, coatings, films, membranes, and composite matrices. The polyarylene ethers of this invention are the polycondensation products from the reaction of either 1,3-bis (4-chloro or fluorobenzoyl) benzene with any one of the following bisphenolic compounds: bis (3-hydroxyphenyl) methane; bis (4-hydroxyphenyl) methane; 1,1-dimethyl-bis (4-hydroxyphenyl)methane, or 9,9-bis (4-hydroxyphenyl) fluorene. Random and block copolymers are also comprehended.

Hergenrother, P. M.↗
NASA NTRS1987

Sol-Gel synthesis of MgO-SiO2 glass compositions having stable liquid-liquid immiscibility

MgO-SiO2 glasses containing up to 15 mol % MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol % MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol % MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol %) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

Bansal, Narottam P.↗
NASA NTRS1986

Structural studies of gels and gel-glasses in the SiO2-GeO2 system using vibrational spectroscopy

GeO2 gel and gels in the SiO2-GeO2 system synthesized by the hydrolytic polycondensation of metal alkoxides have been studied by infrared and Raman spectroscopic techniques. The molecular structures, hydroxyl contents, and crystallinity of gels and gel-glasses in relation to the thermal history and GeO2 concentration were investigated. The binary compositions having up to 70 mol percent GeO2 were examined.

Mukherjee, Shyama P.↗
NASA NTRS1988

Sol-gel synthesis of magnesium oxide-silicon dioxide glass compositions

MgO-SiO2 glasses containing up to 15 mol pct MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol pct MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol pct MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol pct) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

Bansal, Narottam P.↗
NASA NTRS1989

Condensation polyimides

Polyimides belong to a class of polymers known as polyheterocyclics. Unlike most other high temperature polymers, polyimides can be prepared from a variety of inexpensive monomers by several synthetic routes. The glass transition and crystalline melt temperature, thermooxidative stability, toughness, dielectric constant, coefficient of thermal expansion, chemical stability, mechanical performance, etc. of polyimides can be controlled within certain boundaries. This versatility has permitted the development of various forms of polyimides. These include adhesives, composite matrices, coatings, films, moldings, fibers, foams and membranes. Polyimides are synthesized through both condensation (step-polymerization) and addition (chain growth polymerization) routes. The precursor materials used in addition polyimides or imide oligomers are prepared by condensation method. High molecular weight polyimide made via polycondensation or step-growth polymerization is studied. The various synthetic routes to condensation polyimides, structure/property relationships of condensation polyimides and composite properties of condensation polyimides are all studied. The focus is on the synthesis and chemical structure/property relationships of polyimides with particular emphasis on materials for composite application.

Hergenrother, P. M.↗
NASA NTRS1990

Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by sol-gel process

Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water:TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, x ray diffraction, surface area and pore size distribution measurements.

Bansal, Narottam P.↗
NASA NTRS1990

Production of continuous mullite fiber via sol-gel processing

The development of a continuous ceramic fiber which could be used in rocket engine and rocket boosters applications was investigated at the Marshall Space Flight Center. Methods of ceramic fiber production such as melt spinning, chemical vapor deposition, and precursor polymeric fiber decomposition are discussed and compared with sol-gel processing. The production of ceramics via the sol-gel method consists of two steps, hydrolysis and polycondensation, to form the preceramic, followed by consolidation into the glass or ceramic structure. The advantages of the sol-gel method include better homogeneity and purity, lower preparation temperature, and the ability to form unique compositions. The disadvantages are the high cost of raw materials, large shrinkage during drying and firing which can lead to cracks, and long processing times. Preparation procedures for aluminosilicate sol-gel and for continuous mullite fibers are described.

Tucker, Dennis S.↗
NASA NTRS1991

Production of mullite fibers

Disclosed here is a process for making mullite fibers wherein a hydrolizable silicon compound and an aluminum compound in the form of a difunctional aluminum chelate are hydrolized to form sols using water and an alcohol with a catalytic amount of hydrochloric acid. The sols are mixed in a molar ratio of aluminum to silicon of 3 to 1 and, under polycondensation conditions, a fibrous gel is formed. From this gel the mullite fibers can be produced.

Tucker, Dennis S.↗
NASA NTRS1992

Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by the sol-gel process

Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water: TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, X-ray diffraction, surface area and pore size distribution measurements.

Bansal, N. P.↗
NASA NTRS1993

Synthesis and thermal evolution of structure in alkoxide-derived niobium pentoxide gels

Niobium pentoxide gels in the form of transparent monoliths and powder have been synthesized from the controlled hydrolysis and polycondensation of niobium pentaethoxide under different experimental conditions using various mole ratios of Nb(OC2H5)5:H2O:C2H5OH:HCl. Alcohol acted as the mutual solvent and HCl as the deflocculating agent. In the absence of HCl, precipitation of colloidal particles was encountered on the addition of any water to the alkoxide. The gels were subjected to various thermal treatments and characterized by differential thermal analysis, thermogravimetric analysis, x-ray diffraction, and infrared spectroscopy. After drying at 400 C, the gels were amorphous to x-rays. The amorphous powder crystallized into the low-temperature orthorhombic form of Nb2O5 at approximately 500 C, which transformed irreversibly into the high-temperature monoclinic alpha-Nb2O5 between 900 to 1000 C. The kinetics of crystallization of the amorphous niobium pentoxide have been investigated by non-isothermal differential scanning calorimetry. The crystallization activation energy was determined to be 399 kJ/mol.

Bansal, Narottam P.↗
NASA NTRS1995

Subpiosecond Third Order Nonlinear Response in Polythiophene and Thiopene Based Thin Films

Ultrafast relaxation kinetics of the third order nonlinear susceptibility of polythiophene and polycondensed thiophene-based polymer was determined by the forward degenerate four-wave mixing technique. Deep into the absorption band the nonlinear response shows only a fast component (less than 900 fs at 587 nm) while at the edge of the absorption band at 642 nm a much slower and complex decay was measured.

Harris, D.↗
NASA NTRS1997

Three-Dimensional Polybenzobisoxazoles and Polybenzobisthiazoles

Due to the poor compressive strength properties of high performance liquid crystalline polymers such as polybenzobisoxazoles (PBOs) and polybenzobisthiazoles (PBTs), we have prepared homopolymers and copolymers with PBO and PBT pendant groups on a central star-like unit, 2.7-diamino-9,9'-bis(4-aminophenyl)fluorene, in order to improve upon their compressive strength properties. The fluorene moiety was prepared by the reaction of 2,7-dinitro-9-fluorene with aniline and aniline hydrochloride, followed by reduction with palladium on carbon. The central star-like unit was characterized by FTIR, FTNMR, and elemental analysis. The PBO and PBT pendant groups were synthesized by the polycondensation of 4,6-diaminoresorcinol dihydrochloride with terephthaloyl chloride and 2,5-diamino-1,4-benzendithiol dihydrochloride with terephthaloyl chloride in poly(phosphoric acid), respectively. The resulting linear polymers containing the dicarboxylic end groups were attached to the central star-like unit by refluxing with 2,7-diamino-9,9'-bis(4-aminophenyl) fluorene to give the star-like polymers. The star-like PBO and PBT were soluble in methanesulfonic acid. Further characterization of the polymers is ongoing.

Bray, M.↗
DOE OSTI2024

Design of non-fluorinated proton exchange membranes from Poly(Terphenyl fluorenyl isatin) with fluorene-linked sulfonate groups and microblock structures

Proton exchange membranes (PEMs) are essential components in energy storage and conversion devices, such as fuel cells and electrolyzers. Here, in this study, we developed a series of non-fluorinated PEMs from poly(terphenyl fluorenyl isatin) with fluorene-pendent disulfonate groups. These polymers feature a microblock structure composed of hydrophobic blocks, hydrophilic blocks, and alternating blocks, arising from the differences in reactivity, concentration, and solubility between the hydrophobic p-terphenyl and hydrophilic disulfonated fluorene monomers. As a result, the sulfonic acid groups are unevenly distributed along the polymer chains, forming densely charged regions (IEC = 3.52 meq/g) with large ion clusters and lightly charged regions (IEC = 2.16 meq/g) with small ion clusters. This microstructure, combined with the degree of sulfonation, significantly influences the overall properties of the membranes, including robust mechanical strength (47.1–63.2 MPa), high thermal stability (up to 270 °C), low swelling ratio (18–25% at 80 °C), and high proton conductivity (136–169 mS/cm in deionized water at 80 °C). The PFLSH60 membrane demonstrated comparable fuel cell performance to Nafion 212. Its hydrogen crossover current density was more than two times lower (0.86 mA/cm 2 for PFLSH60 compared to 1.83 mA/cm 2 for Nafion 212) under testing conditions of 80 °C and 100% RH. This significantly reduced crossover improves fuel utilization in fuel cell stacks. This work offers valuable insights into the design of robust, high-performance PEMs by systematically analyzing the relationships between membrane structure, properties, and performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Enhancing Biopolyester Backbone Rigidity with an Asymmetric Furanic Monomer

Biobased furanic polyesters can exhibit performance advantages over petroleum-derived polyesters, primarily due to their rigid furan-containing backbones. Herein, we develop two strategies to polymerize methyl 5-hydroxymethyl furanoate to poly(5-hydroxymethyl furanoate) (PHMF), a furan-based polyester with even greater backbone rigidity than poly(ethylene furanoate). Thermal, spectroscopic, and computational investigations of PHMF alongside analogous furan-based and phenyl-based polyesters suggest that the high furan content of PHMF leads to its high glass transition temperature, slow crystallization kinetics, and low amorphous mobility. Molecular dynamics simulations suggest that while the backbone of PHMF is exceptionally rigid, its amorphous phase is denser than its phenyl analog due to noncovalent interchain interactions. Together, these results highlight how asymmetric furan-based monomers can modulate key properties in biobased polyesters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗