High Performance Polymers

A silicon-containing polymer (HMSA), synthesized with n-BuLi, trichloroethylene, dichloromethylsilane, and dimethyldichlorosilane, with three different proportions of Si–H, and its influence on thermal oxidation have been studied. The structures of HMSA were characterized by Fourier transform infrared spectra, ¹H-Nuclear Magnetic Resonance (H-NMR), ¹³C-NMR, ²⁹Si-NMR, and gel permeation chromatography. Thermal and oxidative stabilities were studied by differential scanning calorimetry and thermogravimetric analysis, and the cross-linking reaction mechanisms of the HMSA were discussed. All the polymers exhibited excellent thermal and oxidation resistance; particularly, HMSA-1 showed high heat-resistant and thermo-oxidative stability; the temperatures of 5% weight loss (Td ₅) were 636.3 and 645.5°C, and the residues at 1000°C were 87.07 and 86.23% in nitrogen and air, respectively. This system had excellent thermal and oxidative stability, and through the structure design, control of heat oxidation resistance was realized.

The conventional poly(ether ether ketone) (PEEK) and two other PEEK copolymers (PEEEKK-PEK and PEEEKK-PEEEK) were successfully synthesized and investigated on their thermal stabilities, mechanical properties, and rheological behaviors. Both of the PEEEKK-PEK and PEEEKK-PEEEK were composed of the same chemical components with conventional PEEK (phenyl–ether–ketone equals 3:2:1), but the sequences of their components (phenyl, ether, and ketone) were different. Differential scanning calorimetry analysis and dynamic mechanical analysis indicate that PEEEKK-PEK and PEEEKK-PEEEK have extremely close glass transition temperatures and melting points with conventional PEEK, which suggests their similar operating temperatures. They also process similarly high mechanical properties based on their stress–strain tests. However, PEEEKK-PEK, PEEEKK-PEEEK, and PEEK exhibit significant differences in their rheological behaviors; PEEEKK-PEK even shows an excessively low melt viscosity (51% of PEEK). These results reveal the effects of sequence distribution on polymer properties and thereby demonstrate the processing viscosity of PEEK could be decreased without sacrificing its operating temperature or material performances.

In this work, 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole (2F-Oz) is synthesized and successfully polymerized with 4-(4-hydroxyaryl)-phthalazin-1-one (DHPZ) through polycondensation to produce poly(ether 1,3,4-oxidiazole) containing phthalazinone units (PPEO) with intrinsic viscosity 1.54 dL g⁻¹. A series of sulfonated poly(ether-1,3,4-oxidiazole)s (SPPEOs) with different degrees of sulfonation are prepared via postsulfonation reaction. The chemical structure of PPEO and SPPEOs was characterized through FT-IR and proton nuclear magnetic resonance, respectively. SPPEOs have excellent film-forming properties and readily dissolve in polar aprotic solvents, such as dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), and so on. The water uptake of these SPPEO membranes with measured ion-exchange capacity of 1.13–1.61 mmol g⁻¹ was 15.7–34.1% at 25°C and 17.9–59.8% at 60°C, and swelling ratio was 5.9–14.2% at 25°C and 6.6–18.1% at 60°C, respectively. The proton conductivity of SPPEO-1.61 is 0.045 S cm⁻¹ at 30°C and 0.065 S cm⁻¹ at 80°C, and the tensile strength of the SPPEO-1.61 is 48 MPa, and its elongation at break was 21%. The thermal and chemical stability of the SPPEOs is also examined.

This study focused on the preparation and characterization of silicon–acetylene resin by means of grafting functionalized mesoporous silica. (3-Aminopropyl) triethoxysilane was grafted to silica surface through the hydrolysis reaction to yield mesoporous silica functionalized with (3-Aminopropyl) triethoxysilane (MA). These MA nanoparticles were transferred to the chain of silicon–acetylene resin, poly(m-dietheynylbenzene-methylsilane) (PSA) to yield PSA-g-MA, with the help of the reaction of hydrochloric acid removal. PSA-g-MA was totally characterized by Fourier transform infrared spectroscopy, energy dispersive spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscope, transmission electron microscope, and nuclear magnetic resonance, which certified the success of silica modification and functionalized nanoparticles grafted to chain of PSA. The char content of PSA-g-MA reached to 45% at 1000°C under air atmosphere, and the residual weight was increased by nearly 10%, compared with the unmodified PSA.

Polyimide (PI) aerogels are open-celled materials with high porosity, low density, excellent mechanical property and high thermal stability. Linear PI aerogels exhibit drastic shrinkage during the fabrication process. Cross-linked PI aerogels were usually fabricated by utilizing the costly cross-linking agents such as 1,3,5-triaminophenoxybenzene or octa-(aminophenyl)silsesquioxane. Herein, amino functionalized multi-walled carbon nanotubes (MWCNTs-NH₂) were prepared by amidation reaction; PI/MWCNTs-NH₂ composite aerogels were fabricated by adding MWCNTs-NH₂ to anhydride end-capped poly(amic acid) (PAA), chemical imidization of PAA and supercritical carbon dioxide drying. The microstructures, pore size, elastic modulus, thermal properties and other physical properties of the obtained PI/MWCNTs-NH₂ composite aerogels were investigated. The results showed that MWCNTs-NH₂ could act as a cross-linker of PI because the amino groups of MWCNTs-NH₂ could react with the terminal anhydride groups of PAA. With the addition of MWCNTs-NH₂, the shrinkage of PI/MWCNTs-NH₂ composite aerogels decreased. The densities and Young’s moduli of PI/MWCNTs-NH₂ composite aerogels also decreased. The PI/MWCNTs-NH₂ composite aerogels had coralline-like structure with mesopores (average pore size: 11–20 nm). The PI/MWCNTs-NH₂ composite aerogels also exhibited decent thermal stability and thermal insulating property.

The curing kinetics of two different types of commercial epoxy resins were investigated by means of nonisothermal differential scanning calorimetry (DSC) in this work. The complex curve of measured heat flow of CYCOM 970 epoxy resin was simplified with the method of resolution of peak. Two typical autocatalytic curing reaction curves were gained and the kinetic parameters of the curing process were demonstrated by combination of those two reactions. The Kissinger method was adopted to obtain the values of the activation energy. The parameters of curing kinetic model were acquired according to the fitting of Kamal model. Isothermal DSC curve of CYCOM 970 epoxy resin obtained using the experimental data shows a good agreement with that theoretically calculated. Then, 603 epoxy resin was investigated by the simplified method and the kinetic parameters were received through the same procedure. The nonisothermal DSC curve tested according to the recommended cure cycle of 603 epoxy resin is also consistent with the calculated results. This improved simplified approach provides an effective method to analyze the curing kinetics of the epoxy resins with complex DSC curves as similar to this study.

A new kind of composite membrane consisting of sulfonated poly(ether sulfone) (SPES), poly(vinylidene fluoride) (PVDF), and phosphotungstic acid (TPA) has been prepared and employed as the ion-exchange membrane for vanadium redox flow battery (VRB) application. The addition of the highly crystalline and hydrophobic PVDF effectively confines the swelling behavior of SPES/PVDF/TPA. The composite membrane exhibits one order of magnitude lower vanadium ions permeability and much better single cell performance compared to pristine SPES and Nafion 115 membranes. The single cell with SPES/PVDF/TPA membrane shows much lower capacity loss, higher coulombic efficiency (>97%), and higher energy efficiency (>82%) than which with Nafion 115 membrane. In the self-discharge test, single cell with SPES/PVDF/TPA membrane shows much longer duration in the open-circuit voltage decay than which with Nafion 115 membrane. With all the good performances and low cost, the SPES/PVDF/TPA membrane is expected to have excellent commercial prospects as ion-exchange membrane for VRB system.

In this article, inherent flame-retardant epoxy ether, 9,10-dihydro-9-oxa-10-[1,1-bis(4-glycidyloxyphenyl)ethyl]-10-phosphaphenanthrene 10-oxide (DPBAEP), with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide moieties was synthesized via an economical method and was used to improve the flame retardancy of 4,4′-tetradiglycidyl diaminodiphenyl methane (TGDDM). A series of epoxy resins were prepared and cured with 4,4′-diaminodiphenyl sulfone. The glass transition temperatures (T _g) of resin composites were above 243°C and decreased only slightly after DPBAEP was added. The thermal stabilities under the nitrogen (N₂) and air atmosphere were also measured using thermogravimetric analysis. The results indicated that DPBAEP had a high decomposition temperature and affected the thermal degradation and promoted the charring of resins. When only over 5 wt% of DPBAEP was introduced, the thermosets obtained a high limiting oxygen index value of around 33.0%, achieved vertical burning V-0 rating and presented fast-swelling char barriers. In order to better understand the flame-retardant mechanisms, the residual char was investigated by scanning electron microscopy observation and Fourier transform infrared spectra. We inferred that the phosphorus (P) moieties reacted with the resin matrix, which played a significant role in promoting the formation of char with special structure, as well as making it rich and tough enough. This kind of char barrier could protect the underlying resin matrix against oxygen and heat transfer and inhibited volatile combustible from diffusing to the flame. Hence, thanks to the synergistic effect of P–N and the excellent compatibility, DPBAEP could impart excellent flame retardancy to TGDDM epoxy resin.

Neat polyphenylene sulfide (PPS) fiber and nano titanium-silicon dioxide-modified PPS fibers (A-PPS) were submitted to an over-temperature in air environment at 200, 220, and 240°C for 24, 192, and 360 h, respectively. Molecular and supramolecular structures were characterized by differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). The outside color of the PPS fibers turned yellow and the mechanical properties were reduced after over-temperature, but the performances of the A-PPS fibers were better than that of the neat PPS fibers. The analyses of the molecular and supramolecular structures showed that the temperatures of 200 and 220°C could not change the crystalline form but could increase the crystallinity of the PPS fibers. The crystallization temperature high-shifted and the crystallization FWHM increased after over-temperature. More significant changes at 240°C could be observed such as breaking of the macromolecular chains, mutual cross-linking, and increase of the melting enthalpy to a higher value than the complete crystallization enthalpy of PPS. Cross-linking between the benzene rings and oxidation of the S atoms did not change the PPS crystalline form but decreased the lattice constant. XPS spectra showed that the cross-linking and oxidation of the S atoms of the PPS fibers mainly came from the breaking of the C–S–C bonds, while the break ratio of the C–S–C bonds was relatively smaller in the case of the A-PPS fibers.

New aromatic polyazomethines were synthesized by polycondensation reaction of a diamine containing 1,3,4-oxadiazole ring, namely, 4,4′-diamino-4″-[2-(4-phenoxy)-5-(4-dimethylaminophenyl)-1,3,4-oxadiazole)]triphenylmethane, with terephthalic aldehyde or bis(4-formylphenoxyphenyl)fluorene, by using N-methyl-2-pyrrolidinone (NMP) as solvent. The polymers were easily soluble in polar solvents, such as NMP, N,N-dimethylacetamide, or chloroform, and showed high thermal stability with the initial decomposition temperature above 415°C and the temperature of 10% weight loss in the range of 450–460°C. They exhibited high char yield at 800°C in the range of 52–56%. Optical properties were studied by absorption and photoluminescence spectra. In solution, the polymers presented two absorption maxima in the ranges 273–278 and 330–346 nm and emitted violet-blue light in the range of 413–468 nm, depending on the solvent polarity. The Stokes shift and emission quantum yield values depend on the polymer structure and solvent polarity. The emission intensity in NMP solution was enhanced upon increasing the HCl concentration, while the absorption spectral profile was slightly influenced.

The previously developed TriA-X polyimide resin, consisting of pyromellitic dianhydride/2-phenyl-4,4′-diaminodiphenyl ether; 9,9-bis(4-aminophenyl)fluorene/4-phenylethynylphthalic anhydride (PEPA), was exposed for 3000 h to air at 180, 240, and 270°C or a vacuum environment at 270°C, in order to study its long-term thermal stability. The weight loss and dimensional changes were measured. Elemental analysis was also conducted in order to estimate the TriA-X degradation process. The TriA-X exhibited excellent thermal stability at 180°C and a very small degree of degradation at 240°C, with the degradation becoming significant at 270°C. The latter was primarily dominated by the oxidation of a chain-extension moiety formed by the cure reaction of the end-cap PEPA.

Understanding the effects that monomer chemistries have on material properties allows for fine tuning of polymer synthesis for current and future applications. In order to develop polymeric-based coatings that have minimal surface adhesion characteristics when exposed to a variety of contaminants, a more thorough understanding of fundamental structure–property relationships is needed. In the aeronautics field, one concept to improve fuel efficiency of future aircraft is to modify the wing design to enable laminar flow. There is a concern that contaminants such as insect residue and other debris will adhere to airflow surfaces and have sufficient height to disrupt laminar flow thereby increasing drag with concomitant loss of fuel efficiency. One potential solution would be a polymer surface or coating that prevents or minimizes adhesion of such contaminants. As part of a structure–property relationship study involving modification of surface properties, a series of copolyimides containing both fluorine and silicon surface-modifying agents (SMAs) were prepared and characterized. Based on knowledge of structure–property relationships with polyimides containing either type of SMA, it was hypothesized that the combination of two different SMAs may lead to unique surface properties as the two SMAs competed for surface area at the polymer–air interface. Copolyimides for this study were prepared through a multistep synthesis using an aromatic dianhydride with equimolar amounts of diamino functionalities comprised of an aromatic diamine along with two SMAs. Films were cast from copoly(amide acid) solutions that were subsequently thermally imidized under a nitrogen atmosphere. Polyimide films and coatings were characterized using differential scanning calorimetry, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, contact angle goniometry, scanning electron microscopy, and energy-dispersive X-ray spectroscopy to determine chemical, thermal, and surface properties. Select samples were subject to high velocity insect impacts in a small-scale wind tunnel and the resulting residues were characterized for height and surface area and compared to those of a control surface.

Silicone elastomer (SiR) nanocomposites were prepared using multiwalled carbon nanotubes (MWCNT) and nano-graphite (NG). The morphology of the SiR nanocomposites has been studied using scanning electron microscopy and high-resolution transmission electron microscopy techniques. Detailed analysis of the morphology reveals a uniform distribution of the MWCNT and NG filler particles in the silicone matrix. On increasing the filler loading, a continuous network structure is formed and aggregation takes place. The effect of the MWCNT and NG loadings on the thermal properties of the silicone elastomer has been investigated. The thermal properties of the SiR nanocomposites were measured by a thermal properties analyzer based on the transient hot-wire method. Studies also suggest that incorporation of nanoparticles improves the thermal conductivity of SiR nanocomposites. The thermal conductivity of SiR nanocomposites increased from 0.200 W/(m K) to 0.440 W/(m K) and to 0.310 W/(m K) for 6 wt% MWCNT and NG loadings, respectively. Because of the positive temperature coefficient and the conductive nature of the nanoparticles, the thermal conductivity of the material increased on increasing the temperature. The thermal diffusivity and the volumetric heat capacity of the SiR nanocomposites were measured. The thermal diffusivity of the SiR nanocomposites increased from 0.1194 mm²/s to 0.3209 mm²/s and to 0.2050 mm²/s for 6 wt% MWCNT and NG loadings, respectively. This indicates that the temperature response becomes faster with MWCNT and NG loadings. The volumetric heat capacity of the silicone elastomer nanocomposites decreased from 1.80 MJ/(m³K) to 1.34 MJ/(m³K) and to 1.40 MJ/(m³K) for 6 wt% MWCNT and NG loadings, respectively. Thus, MWCNT particles are more effective in increasing the thermal conductivity and diffusivity of the SiR nanocomposites, when compared to NG fillers at any loading.

In this study, asymmetric polyphenylene-ether-ether-sulfone (PEES) ultrafiltration (UF) membranes containing graphene oxide (GO) were prepared via non-solvent-induced phase separation process and N-methyl pyrrolidone was used as a solvent. The synthesis of GO was confirmed by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis. The morphology of the prepared GO nanosheets was observed by field emission scanning electron microscope (FESEM) and transmission electron microscope. The membranes prepared with increasing concentrations of GO nanosheets were characterized by attenuated total reflectance-FTIR, SEM, atomic force microscopy (AFM), contact angle, and UF studies. The FTIR spectra of the GO embedded membranes reveal large amounts of –OH groups present due to the existence of GO nanosheets which improved its surface hydrophilicity. The contact angle of PEES/GO membrane was significantly lower than PEES membrane. The SEM pictures showed that PEES/GO UF membranes had a sponge-like substructure with the increased porosity and pore size. An AFM topography imaging showed that roughnesses of the modified membranes were improved compared to the pristine PEES membrane. The UF studies showed that the pure water flux (J_W ) and the bovine serum albumin flux (J_P ) were increased with the incorporation of GO into the blend solution. For the membrane with 0.1% GO content, J_W increased by 75% and J_P improved twofold which correspond to the maximum values of 186 and 113 L m⁻² h⁻¹, respectively. Furthermore, the flux recovery ratio results suggested that PEES/GO membranes have better antifouling characteristics due to the changes in membrane morphology and surface hydrophilicity.