The polymerization behavior and thermal properties of benzoxazine based on o-allylphenol and 4,4′-diaminodiphenyl methane

Three bifunctional benzoxazines (oAP-ddm, oC-ddm, and P-ddm) were synthesized from 4,4′-diaminodiphenyl methane, formaldehyde, and three phenols, namely o-allylphenol, o-cresol, and phenol. The polymerization temperatures and activation energies of oAP-ddm and oC-ddm are very similar and higher than those of P-ddm; however, their reaction enthalpies exhibit inverse behavior. The storage moduli of the corresponding polybenzoxazines, PoAP-ddm, PoC-ddm, and PP-ddm, are approximately 2.1, 3.2, and 2.9 GPa at 25 °C, respectively, and their glass transition temperatures are 139, 166, and 198 °C, respectively. The thermal stabilities of PoAP-ddm and PoC-ddm are similar and lower than that of PP-ddm. The results indicate that polybenzoxazines based on ortho-substituted phenols provide higher flexibility than their counterparts prepared from unsubstituted phenol.     

Pervaporation of water/acetic acid through polyimide membranes from 3,3′, 4,4′-benzophenone tetracarboxylic dianhydride and 4,4′-oxydianiline

Summary Pervaporation performance of polyimide (PI) membrane from 3,3, 4,4-benzophenone tetracarboxylic dianhydride (BTDA) and 4,4-oxydianiline (ODA) was investigated at 80wt% feed acetic acid concentration and at 65°C. Imide contents in PI film were estimated by thermogravimetric analysis (TGA) method. The separation factor of PI membrane increases with the degree of imidization, while the flux was almost constant. The separation factor toward water through PI-94 membrane was about 417 with the flux of 47 g/m². hr measured at 65°C and with 80wt% acetic acid as a feed. PI-94 showed the best pervaporation performance toward the separation of water from acetic acid solution among the PI membranes investigated. The swelling behaviors at various feed concenration were also examined.     

Effect of chemical structure of aromatic dianhydrides on the thermal, mechanical and electrical properties of their terpolyimides with 4,4′-oxydianiline

Aromatic terpolyimides were synthesized by the reaction of 3,3′,4,4′-oxydiphthalicdianhydride(ODPA), 3,3′,4,4′-biphenyldianhydride(BPDA) and 3,3′,4,4′-benzophenonetetracaboxylicdianhydride(BTDA) with 4,4′-oxydianiline(ODA) via thermal imidization with the view to enhance their tensile properties without compromising thermal properties compared to their homo and copolyimides. Their films were characterized by FTIR, TGA, DSC and XRD. Their FTIR spectra established formation of polyimide by the characteristic vibrations at 1375cm⁻¹(C-N stretch) and 1113 cm⁻¹(imide ring deformation). TGA results showed imidization of residual polyamide acid close to 250 °C and decomposition of polyimides at about 540 °C. XRD results showed amorphous nature for all terpolyimides. Their tensile strength and tensile modulus were higher than either homo or copolyimides. Incorporation of BPDA, without bridging groups between the aromatic rings into the backbone of ODPA/BTDA-ODA is suggested as the cause for such an enhancement. Such terpolyimide can find application as adhesives in making flexible single/multilayer polyimide metal-clad laminates in flexible printed circuits and tape automated bonding applications. In addition, the terpolyimide, BPDA/BTDA/ODPA-ODA (mole ratio 0.5:0.25:0.25:1), showed low dielectric constant (3.52) as BPDA could offer slight rigidity by which the orientation of polar groupings could be reduced.     

Chemical reactions,thermal and mechanical properties of epoxy — Polycarbonate blends cured with aromatic amines

Bisphenol-A polycarbonate (PC) has been incorporated into epoxy resin cured with 4,4-diaminodiphenyl sulphone (DDS) and 4,4'-diaminodiphenyl methane (DDM). IR spectra reveal that transesterification and transamidation occur between the carbonate group of PC and the hydroxyl group of cured epoxy resin for the DDM-cured system, and that only transesterification occurs for the DDS-cured system. Scanning electron micrographs (SEM) show no evidence of phase separation in these cured systems, which is an indication of full miscibility between the bisphenol-A monomers and PC-oligomers with the copolymer network. The mechanical strength and glass transition temperature (T_g) fluctuate with PC content, whereas the flexural modulus shows a steadily increasing tendency.     

Synthesis and properties of poly(ester imide) copolymers from 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis(trifluoromethyl)benzidine,and 4-aminophenyl-4′-aminobenzoate

A series of poly(ester imide) (PEsI) copolymers were synthesized using 3,3′,4,4′-biphenyltetracarboxylic dianhydride (4,4′-BPDA), 2,2′-bis(trifluoromethyl)benzidine (TFMB), and 4-aminophenyl-4′-aminobenzoate (APAB) as the monomers. Wide-angle x-ray diffraction results revealed that the average interchain distances of these polymers ranged from 4.6 to 5.7 Å, increasing with the increase of TFMB contents. PEsI-0.3 and PEsI-0.4 exhibited a glass transition temperature (T_g) of 445 and 455°C, respectively, while no distinctive T_g was observed for the PEsI copolymers when the APAB content was >50 mol%. The coefficients of thermal expansion (CTE) of these PEsI copolymers ranged from 3.8 to 24.2 ppm K⁻¹, increasing with the increase of TFMB contents. The PEsI copolymers exhibited a modulus of 5.7–7.8 GPa, a tensile strength of 282–332 MPa, and an elongation-at-break of 10.2%–23.3%. Furthermore, these copolymers exhibited a dielectric constant of 2.53–2.76, and a low dissipation factor (D_f) of 0.0026–0.0032 at 10 GHz in dry state. Because of their excellent combined properties, these PEsI copolymers are promising candidates as dielectric substrate materials for the applications in next generation flexible printed circuit boards operating at high frequencies.     

Synthesis,characterization and properties of polyimides from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride and imidazole-blocked 2,5-bis[(n-alkyloxy)methyl]-1,4-benzenediisocyanates

Summary By the solution condensation of 3,3,4,4-benzophenonetetracarboxylic dianhydride (BTDA) with imidazole-blocked 2,5-bis[(n-alkyloxy)methyl]-1,4-benzenediisocyanates (C_m-BDIs) a series of aromatic polyimides (C_m-BP-PIs) having flexible (n-alkyoxy)methyl (-CH₂O-n-C_mH_2m+1, m=4, 6, 8) side chains were prepared and characterized by IR- and ¹H-NMR spectroscopy and their properties were measured and discussed in respect to the effects of side chains. Inherent viscosities of the polymers were in the 0.23–0.34 dL/g range. All the polymers were highly soluble in N,N-dimethylpropyleneura(DMPU) and C₆- and C₈-BP-PIs even in CHCl₃ at room temperature. UV-VIS spectra showed that the -electrons are delocalized along the main chain. TGA studies showed a two-step pyrolysis behavior and in DSC Tg's of C₄-, C₆- and C₈-BP-PIs were determined to be 184, 135 and 127 °C, respectively. Wide-angle X-ray diffractometry for as-polymerized samples revealed a quite low crystallinity with only loosely developed layered structure.     

Influence of α-Si3N4 coarse powder on densification,microstructure, mechanical properties,and thermal behavior of silicon nitride ceramics

Silicon nitride (Si₃N₄) ceramics, with different ratios of fine and coarse α-Si₃N₄ powders, were prepared by spark plasma sintering (SPS) and heat treatment. Further, the influence of coarse α-Si₃N₄ powder on densification, microstructure, mechanical properties, and thermal behavior of Si₃N₄ ceramics was systematically investigated. Compared with fine particles, coarse particles exhibit a slower phase transition rate and remain intact until the end of SPS. The remaining large-sized grains of coarse α-Si₃N₄ induce extensive growth of neighboring β-Si₃N₄ grains and promote the development of large elongated grains. Noteworthy, an appropriate number of large elongated grains distributed among fine-grained matrix forms bimodal microstructural distribution, which is conducive to superior flexural strength. Herein, Si₃N₄ ceramics with flexural strength of 861.34 MPa and thermal conductivity of 65.76 W m⁻¹ K⁻¹ were obtained after the addition of 40 wt% coarse α-Si₃N₄ powder.     

Mechanical and thermal behavior of modified epoxy–novolak film adhesives

Modified epoxy-based film adhesives were developed for bonding structural joints. Film adhesives with different compositions were prepared by hot pressing the molten resins. Peel and shear tests were carried out to evaluate the adhesion properties. Dynamic mechanical thermal analyses were conducted to follow the changes in the adhesive structure and also the trend of impact strength. Incorporation of thermoplastic poly(vinyl butyral) (PVB) into an epoxy- novolak combination resulted in higher cohesive strength, better film-forming ability, enhanced adhesive shear and peel strengths, but decreased thermostability. However, due to the lower chemical functionality of PVB, a lower crosslink density was achieved. Incorporation of a small amount of ethylene glycol dimethacrylate (EGDM) as a flexibilizer led to improved mechanical properties, easy handling and facile application. Finally, good shear strength retention up to 200 °C for 1 h was observed in the case of EGDM-modified adhesives.     

Effect of number of graphene layers on mechanical and dielectric properties of graphene–epoxy nanocomposites

In this study, mechanical and dielectric properties of epoxy nanocomposites with two types of graphene, <?10 layer stacks (GEC10) and <?30 layer stacks (GEC30) were investigated. Results showed that the number of graphene layers remarkably affected the dielectric properties of epoxy nanocomposites. The real and imaginary parts of relative permittivity and loss tangent of GEC10 samples were noticeably enhanced and reached to 1.29, 20 and 15.6 times respectively for 1?wt-% graphene sample compared to GEC30 samples. Meanwhile, tensile tests showed a peak for tensile strength of GEC10 and GEC30 samples with 0.1?wt-% graphene, which improved by 13 and 7.9% with respect to pure epoxy respectively. In addition, flexural properties did not change significantly compared to the pure epoxy.     

Effect of zirconia content on mechanical and thermal properties of mullite–zirconia composite

Abstract

Mullite–zirconia composites were prepared by adding various zirconia contents in the mullite ranging from 0 to 30 wt-% and sintering at 1400–1600°C for 2 h. The phase composition examined by X-ray diffraction showed that mullite was the major phase combined with developed t-ZrO₂ and m-ZrO₂ phase as a function of zirconia content, especially at 1600°C, wherein m-ZrO₂ predominated. Density increased when the zirconia content and sintering temperature were increased ranging from 2·2 to 3·53 g cm^?3. The morphology of mullite grain showed elongated grains, whereas dispersed zirconia showed equiaxed and intergranular grains. Flexural strength was continuously improved by adding zirconia during the sintering temperature ranging from 1400 to 1500°C, whereas flexural strength was initially improved up to 5 wt-% of zirconia addition and deteriorated with more than 5 wt-% of zirconia content during sintering between 1550 and 1600°C. The maximum strength, 190 MPa, was obtained when sintering mullite with 30 wt-% of zirconia content at 1500°C. The degradation of strength at high sintering temperature may be a result from more occurrence of m-ZrO₂ phase. Thermal expansion of sintered specimens indicated linear change and hysteresis loop change. The hysteresis loop obtained with increased zirconia content resulted in the t–m phase transformation. Martensitic start temperature M_s was determined to be 530°C for 15 wt-% zirconia sintered at 1500°C, implying that the t–m phase transformation occurred.     

Effect of zeolitic metal–organic framework on thermal,mechanical, and electrical properties of Ca/Zn-stabilized polyvinyl chloride

In order to enhance the heat stability of polyvinyl chloride (PVC), several heat stabilizing parameters such as metal content, antioxidant percentage, primary-to-secondary antioxidant ratios, stearic-to-acetylacetonate ratio, the amounts of pentaerythritol and β-diketone were studied using oven and Congo red tests. Results indicated that the percentage contribution of the calcium-to-zinc molar ratio in the static heat stability was 60.78%. Due to the synergistic effects of the calcium/zinc stabilizer and the zeolitic metal–organic framework (MOF) as an effective co-stabilizer, the heat stability was increased from 109 to 148 min. The EDX analysis was carried out to determine the mechanism of HCl gas absorption by the zeolitic imidazolate framework-8 (ZIF-8) existing in the PVC compound. Furthermore, the Ca/Zn thermal stabilizer showed poor electrical insulating properties, but the ZIF-8 improved electrical resistivity of the PVC compounds. Volume resistivity of ZIF-8 was significantly higher than that of the commonly used Ca/Zn stabilizers. Dynamic mechanical thermal analysis and tensile test of the PVC compound containing the ZIF-8 showed increased T_g and enhanced toughness.     

Two d10 coordination polymers based on 4,4′-(hexafluoroisopropylidene)diphthalic acid: Syntheses,structures and physical properties

Two novel coordination polymers, [Zn₂(FA)(4,4′-bipy)₂]·2H₂O (1) and Cd₂(FA)(2,2′-bipy) (2), (H₄FA = 4,4′-(hexafluoroisopropylidene)diphthalic acid, 4,4′-bipy = 4,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine), have been synthesized under hydrothermal conditions, and their structures were determined by single-crystal X-ray diffraction. Polymer 1 features an unusual three-dimensional (3D) network with (4 · 6² · 8³)(4² · 6² · 8²) topology. Polymer 2 has a complicated 3D framework and crystallizes in non-centrosymmetric space group (Fdd2) belonging to polar point group (C_2v), which displays a strong SHG response and ferroelectric properties. Moreover, the luminescent properties of 1 and 2 have also been investigated.     

Syntheses and properties of aromatic polyamides derived from 4,4′-oxydibenzoic acid and aromatic diamines

A series of aromatic polyamides were synthesized by direct polycondensation of 4,4-oxydibenzoic acid with various aromatic diamines inN-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride, using triphenyl phosphite and pyridine as condensing agents. The resultant polyamides had inherent viscosities of 0.21-1.48 dL/g. Most of the polymers were organo-soluble and could be solution-cast into flexible and strong films. The glass transition temperatures (T_gs) of most polyamides could be determined with the help of differential scanning calorimetry (DSC) traces, which were recorded in the range of 170–275 °C. Thermogravi metric data of these polymers indicated that most of the polyamides showed no significant weight loss before 450 °C in either air or nitrogen atmospheres.     

Synthesis and modification of silica-based epoxy nanocomposites with different sol–gel process enhanced thermal and mechanical properties

This research article describes the results of nano-silica composites filled with different epoxy contents containing nano-SiO₂ particles from (5–25 wt%). Reinforcing hybrid composites enhance thermal and mechanical properties to achieve vital and sustainable products. Silica-based nanocomposites with high purity were prepared and used for the surface modification of nanosized silica particles. The surface structure's composition and physical properties of modified nano-SiO₂ particles were characterized through Fourier transferred infrared spectrometer, X-ray photoelectron spectroscopy, thermogravimetric analyzer, and scanning electron microscopic. Silica-based nanocomposites were prepared by incorporating of modified nano-SiO₂ as an enhancing filler. The morphology of fracture surface and dynamic mechanical properties were investigated. Results showed that the silica-based epoxy nanocomposites are bearing a long chain structure that could improve the compatibility of silica nanocomposites with epoxy resin and contribute to a better dispersion state in the matrix, which enhanced the overall performance of epoxy-cured products.     

Oxidation,mechanical and thermal properties of hafnia–silicon carbide nanocomposites

Dense nanocomposites constituted from 70/30 vol% of hafnia–silicon carbide and were prepared by spark plasma sintering. Silicon carbide suppresses grain growth. The fracture strength of as prepared composites is 400–600 MPa. Oxidation up to 1600 °C in air for 10 h has minor influence on the mechanical strength, which is ascribed to the dense nature of the oxidation scale. The high density of the oxidation scale is attributed to a volume increase when silicon carbide oxidizes and reacts with hafnia to form hafnium silicate. The composite has a thermal conductivity of 14 W m⁻¹ K⁻¹ at room temperature. Design approaches for further enhancement of ultrahigh temperature properties of oxide/non-oxide composites are discussed.     

Effects of vinyltrimethoxy silane on thermal properties and dynamic mechanical properties of polypropylene–wood flour composites

The viability of vinyltrimethoxy silane was investigated as a coupling agent for the manufacture of wood–plastic composites (WPC). The effect of silane pretreatment of the wood flour on the thermal and the dynamic mechanical properties and thermal degradation properties of the composites were studied. Moreover, the effect of organosilane on the properties of composites was compared with the effect of maleated polypropylene (MAPP). DSC studies indicated that the wood flour acts as a PP-nucleating agent, increasing the PP crystallization rate. In general, pretreatment with small amounts of silane improved this behavior in all the WPCs studied. Thermal degradation studies of the WPCs indicated that the presence of wood flour delayed degradation of the PP. Silane pretreatment of the wood flour augmented this effect, though without significantly affecting cellulose degradation. Studies of dynamic mechanical properties revealed that the wood flour (at up to 30 wt %) increased storage modulus values with respect to those of pure PP; in WPCs with a higher wood flour amount, there was no additional increase in storage modulus. Pretreatment of the wood flour with silane basically had no effect on the dynamic mechanical properties of the WPC. These results show that with small amounts of vinyltrimethoxy silane similar properties to the MAPP are reached. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Compositional tailoring effect on crystal structure,mechanical and thermal properties of γ-AlON transparent ceramics

In view of the practical application of γ-AlON as a promising transparent structural ceramic, in-depth insight into its mechanical and thermal properties is essential. The solid-state MAS NMR technique was combined with XRD Rietveld refinement to confirm the crystal structure of Al_(8+x)/3O_4-xN_x (x = 0.299–0.575). These structural parameters were further applied to predict hardness and elastic properties based on theoretical exploration, which are in good agreement with the experimental values. A slight enhancement of mechanical properties with increasing nitrogen concentration is attributed to the stronger chemical bond in octahedra. The experimental thermal conductivity of γ-AlON transparent ceramics was improved slightly with the rise of x in the temperature range from 298 K to 1074 K. The intrinsic lattice thermal conductivity was determined by eliminating the extrinsic phonon scattering as well as the thermal radiation. The reason for the discrepancy between experimental and intrinsic thermal conductivity was revealed. The present methods provided powerful and accessible guidelines in optimizing the mechanical and thermal properties of oxynitride materials.     

Optical,electrical, mechanical,and thermal properties and non-isothermal decomposition behavior of poly(vinyl alcohol)–ZnO nanocomposites

Iranian Polymer Journal - Poly(vinyl alcohol) (PVA) nanocomposites incorporated with ZnO nanofiller were prepared and examined to study the influence of nanofiller on their properties. All the...     

Effect of core–shell rubber toughening on mechanical,thermal, and morphological properties of poly(lactic acid)/multiwalled carbon nanotubes nanocomposites

The effect of core–shell rubber (CSR) toughening on mechanical and thermal properties of poly(lactic acid)/multiwalled carbon nanotubes (PLA/CNT) nanocomposites were investigated. The nanocomposites were prepared by direct melt blending method in a counter-rotating twin-screw extruder. The contents of CSR were varied between 5 and 20 wt % while the content of CNT was kept at 5 phr. The extruded samples were injection molded into the desired test specimens for mechanical and thermal properties analysis. The impact strength of PLA/CNT increased with increasing CSR content with concomitant decrease in tensile strength and modulus. Interestingly, the flexural strength increased at low CSR content before decreasing at 15 and 20% content. Differential scanning calorimetry analysis on the second heating cycle shows no crystallinity content for PLA/CNT and all CSR toughened PLA/CNT nanocomposites, while thermogravimetric analysis shows lower thermal degradation of all CSR toughened PLA/CNT as compared to PLA/CNT nanocomposite. This study reveals significant correlation between CSR loading with the mechanical and thermal properties of the nanocomposites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47756.     

Binuclear, 2D grid and 3D interlocking coordination polymers based on 1,2,4,5-benzenetetracarboxylic acid and 4,4′-azobispyridine

Three new nickel(II) complexes [Ni₂(btec)(azopy)₂(H₂O)₈]·2H₂O (1), {[Ni(H₂btec)(azopy)(H₂O)₂]·(azopy)}_n (2) and {[Ni₄(btec)₂(azopy)₃(H₂O)₁₀]·8H₂O}_n (3) (H₄btec = 1,2,4,5-benzenetetracarboxylic acid; azopy = 4,4′-azobispyridine) have been synthesized by tuning the reaction temperature and the metal–ligand ratio. They were characterized by single-crystal X-ray diffraction and elemental analysis. 1 shows a binuclear structure, 2 exhibits a 2D grid, and 3 features an interesting 3D framework with (6³)(4.6²)(4².6².8²) topology formed by two types of interlocked 2D layers.