Polymer composite materials based on thermoset epoxy binders modified with diamond-containing nanofillers

Structural features and physicochemical properties of promising diamond-containing modifier fillers for industrial polymers, namely, detonation nanodiamonds and nanodiamond soot, are considered. Experimental results demonstrating the possibility to create prepregs with the use of the carbon fabric 1.5 К and a detonation-diamond soot-modified binder based on the epoxy-resin mixture Epikote828/Epikote154 with an anhydride-type curing agent are presented. The rheological characteristics of the diamond-sootmodified binder remain practically the same after storage for 2 or 3 days at room temperature. The dependence of the glass-transition temperatures of the binders on the content of diamond soot in the concentration range 0.025–0.1 wt % is studied, and the correlation between these results and the mechanical characteristics (breaking strength, flexural strength, and crack resistance) of the cured binders is ascertained. Within the entire range of diamond-soot concentrations, the parameters of gelation are determined and the activation energies of this process are calculated.     

Preparation and characterization of composite resin by vinyl chloride grafted onto poly(BA-EHA)/poly(MMA-St)

Crosslinked poly(butyl acrylate-co-2-ethylhexyl acrylate)/poly(methyl methacrylate-co-styrene) (ACR I) latex was synthesized by multi-stage emulsion polymerization. A series of grafting vinyl chloride (VC) composite latices were prepared by emulsion copolymerization in the presence of core-shell ACR I latex. The effects of ACR I amount and its core/shell ratio on particle diameters of the composite latices and mechanical properties of the prepared materials were investigated. The grafting efficiency (GE) of VC grafted onto ACR I increases with an increasing ACR I content. Transmission electron microscope (TEM) study indicates that ACR I latex particles have a regular core-shell structure obviously. However, when styrene content in the shell of ACR I is more than 70 percent of the shell by weight, ACR I latex particles have an irregular core-shell morphology like sandwich. The composite latex particles synthesized by core-shell ACR I latex grafting VC have a clear three-layered core-shell structure. Dynamic mechanical analysis (DMA) study reveals that the compatibility between ACR I and PVC is well improved. With increasing ACR I content, the loss peak in low temperature range for every composite sample becomes stronger and stronger and gradually shifts to a higher temperature. Scanning electron microscope (SEM) graphs showed that the fractured surface of the composite sample exhibited better toughness of the material. TEM graphs showed that ACR I was uniformly dispersed in the PVC matrix.     

Kevlar 49 composite performance: Dependence on thermoset resin microstructure

Molecular structures for cured, thermoset resins have been examined by analyses of resin extracts by gel permeation chromatography. Numerical interpretation of leached oligomeric fractions coupled with kinetic reaction theory yields microscopic estimates of the network's structure, including crosslink average molecular weight. Leached monomeric fractions describe extent of cure. Analyses of test data incorporate irreversible, mechanical deformations for neat resin castings and for filament wound, Kevlar 49 composites. Heat distortion temperatures correlate with crosslink architecture. Short beam shear strength data for naval ordinance laboratory rings and pressure vessel burst performance are examined in terms of the resin's molecular structure. Variations in resin cure observed by positive feedback via chromatography indicate fluctuations in extent of crosslink development. Test specimen performance correlates with these microscopic, molecular distributions. Resin applications include filament wound composites for the aerospace industry, anhydride cured epoxies, and amine cured epoxies. The former resin is an elastic body at ambient test conditions. A third resin, a crosslinked resin of 1,2 polybutadiene/t-butylstyrene, is in final developmental stages and may exhibit a higher degree of viscoelastic behavior.     

Epoxidized poly(decenyloxazoline) in thermoset coatings

The side chain double bonds of poly(decenyloxazoline) were epoxidized using standard techniques. The epoxidation was facile and a high percentage of the double bonds were converted to oxirane groups. Films of the epoxidized resin were cured at an elevated temperature with either diamine or anhydride crosslinking agents. Both types of crosslinking agents yielded cured films with good solvent resistance, high hardness, and high gloss. The films cured with the anhydride crosslinkers and the higher molecular weight diamine had better properties than the films cured with the low molecular weight diamine. This could be because some of the low molecular weight diamine was lost due to evaporation during the cure cycle, which would result in lower crosslink density.     

纳米腐植酸/丙烯酸-丙烯酰胺-蒙脱土复合型树脂的制备与表征

以N,N-亚甲基双丙烯酰胺为交联剂,过二硫酸钾为引发剂,丙烯酸、丙烯酰胺、纳米腐植酸及改性蒙脱土为原料,采用水溶液聚合法制备了丙烯酸-丙烯酰胺/纳米腐植酸基复合型树脂。通过单因素及正交实验系统考察了单体比(质量比)、纳米腐植酸用量、反应温度等因素对复合型树脂吸液倍率的影响。最适宜制备工艺条件为:单体比3∶7,纳米腐植酸用量为15%,反应温度65℃,中和度80%,交联剂0.05%,引发剂1.0%,所制备的复合型树脂吸水和吸盐倍率分别为998.90 g/g及102.59 g/g。用FT-IR,SEM及TG-DSC等对产物进行表征,结果表明:纳米腐植酸与丙烯酰胺发生接枝反应,产生了醚键;其表面结构疏松且粗糙,呈现较多孔洞、空隙及凹坑;热稳定性较好。     

环氧树脂基阻尼复合材料研究进展

简要阐述了高聚物阻尼材料的阻尼机理,综述了环氧树脂胶液的阻尼性能及其影响因素、纤维增强环氧树脂阻尼复合材料以及无机填料/环氧树脂阻尼复合材料的研究状况,指出了环氧树脂基阻尼材料的发展方向及前景。     

Preparation and characterization of poly(vinyl alcohol)‐modified red mud composite materials

A series of polymer–acid‐modified red mud composite (PRM) materials that consist of poly(vinyl alcohol) (PVA) and layered Red mud (RM) are prepared by effectively dispersing organic PVA matrix into the inorganic layers of modified RM via a conventional solvent casting technique. The as‐synthesized PRM materials are typically characterized by Fourier transformation infrared (FTIR) spectroscopy and wide‐angle X‐ray diffraction. The morphological image of as‐synthesized materials is studied by scanning electron microscopy (SEM) and optical microscope (OM). Effects of the material composition on the thermal stability and optical clarity of PVA along with a series of PRM materials freestanding film are also studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and UV–vis transmission spectra, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 238–243, 2007     

采用超临界/亚临界水回收热固性树脂基复合材料

综述了近年来国内外研究者利用超临界/亚临界水分解热固性树脂基(如不饱和聚酯,酚醛树脂,环氧树脂等)复合材料的研究,该方法可将热固性树脂基复合材料分解为单体或低聚物,具有环保、经济、安全的特点,作为一种新兴技术,具有较好的发展前景。     

Synthesis,characterization, and cure of allyl and propargyl functionalized indene as a thermoset composite matrix resin

Two highly functionalized resins were synthesized by the phase transfer reaction of indene with propargyl bromide or allyl chloride in the presence of strong base. The resins consisted of a mixture of tri- and tetrafunctional indenes with 60–80% of the product being tetrafunctional. The allylated (AL) and propargylated (PL) indene resins were thermally cured without added catalysts. Both resins exhibited a broad, highly exothermic cure with a peak energy at 320°C for AL resin and 282°C for PL resin. Thermal degradation of cured AL resin was found to begin at approximately 400°C with a carbon yield of 20% of its initial weight at 1000°C. Carbon yields for cured PL resin were excellent, with 68% retention of weight at 1000°C. Unidirectional, carbon fiber composites were fabricated from the substituted indene resins. AL–carbon fiber composites gave modulus values of 126 GPa and strength values of 967 MPa, while PL–carbon fiber composites gave modulus values of 116 GPa and strength values of 935 MPa in three-point bending tests. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 475–482, 1998     

Influence of the chemical modification of phenoxy resin on its miscibility with poly(2-vinyl pyridine)

The influence of the chemical modification of the hydroxyl groups of phenoxy resin (PH) by benzoate, acetate and methoxy groups on its miscibility with poly(2-vinyl pyridine) (P2VPy) is investigated. Both DSC and FTIR results permit the definition of three distinctive regions: up to 40% modification all 50/50 blends are miscible; between 40 and 55% modification all blends present partial miscibility and at higher than 55% modification the blends are totally immiscible. Specific interactions between the hydroxyl groups of PH and the amine groups of P2VPy are put forward as an explanation for these observations.     

Synthesis and characterization of poly (amide-imide-imide)s based on diacids with bulky m-chloro phenyl moiety and rigid pyridine moiety

A series of novel aromatic diamines containing kinked m-chloro phenyl moiety was synthesized by the reaction of m-chloro benzaldehyde with 2,6-dimethyl aniline. The tetraimide diacid was synthesized by using the prepared diamine with benzophenone tetracarboxylic acid dianhydride (BPTDA) and p-amino benzoic acid. The polymers were prepared by treating the tetraimide diacid with different aromatic diamines. The structures of the monomers and polymers were identified by ¹H-NMR, FTIR,¹³C-NMR and elemental analysis. The polymers showed excellent thermal stability, solubility and mechanical properties. Their structure–property relationship was studied by comparing these m-chloro polymers with polymers containing rigid Pyridine moiety.     

Micromechanical behavior of impact modified poly(ethylene terephthalate)

The micromechanical behavior of poly(ethylene terephthalate), PET, modified with a metallocene polyolefin copolymer (mPE) was investigated. Uniaxial deformation tests were performed using a tensile stage in a scanning electron microscope. This technique allowed the identification of the main deformation mechanisms that are associated with energy dissipation and toughness improvement. The poly(ethylene terephthalate) was blended with 5 wt% mPE by single‐screw extrusion. Films with thicknesses ranging from 200 to 500 μm were produced. Observation of the surfaces of the films during uniaxial deformation revealed the sequence of events leading to the full yielding of the matrix. In the early stages of deformation, the particles deform together with the matrix. As the deformation is increased, cavitation inside the particles occurs and fibrillation at the particle/matrix interface is observed, as well as the onset of shear banding. In order to study the effect of interfacial adhesion of the deformation mechanisms, the PET/mPE blends were compatibilized by grafting with glycidyl methacrylate (GMA). The reduction of the particle size was significant, which is indicative of the efficiency of GMA grafting in this type of blend. In this case, the particles were difficult to detect on the surface. Cavitation and shear banding occurred simultaneously. A similar behavior was observed in the case of oriented blends.     

A conducting composite based on poly(N‐vinylcarbazole)–formalin resin and acetylene black

A poly(N‐vinylcarbazole) (PNVC)–formalin (FO) resin (PNVC‐FO) was prepared via copolycondensation between N‐vinylcarbazole (NVC) and FO in the presence of dry HCl gas in toluene medium at 110°C. A highly conducting composite of PNVC‐FO resin with nanodimensional acetylene black (AB) was prepared by carrying out the polycondensation reaction in presence of a suspension of acetylene black (AB) in toluene. The inclusion of PNVC in the PNVC‐FO‐AB composite was confirmed by FT‐IR analysis. Scanning electron microscopic analyses of PNVC‐FO resin and PNVC‐FO‐AB composite revealed formation of spherical particles and aggregates of irregular shapes respectively. Thermogravimetric analyses revealed the overall stability order as: AB > PNVC‐FO‐AB composite > PNVC‐FO resin > PNVC homopolymer. In sharp contrast to PNVC and PNVC‐FO resin, which were both nonconducting (10^?12 to 10^?16 S/cm), the conductivity of the composites reached values between 0.75 S/cm and 6.54 S/cm corresponding to AB loading of 28–49 wt % respectively. Temperature versus conductivity studies revealed an initial increase in conductivity upto 200°C and current–voltage characteristics of the PNVC‐FO‐AB composite showed a linear trend consistent with Ohmic behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3837–3843, 2007     

Hybrid materials based on metal oxides and poly(organophosphazenes)

In this paper the sol-gel preparation of hybrid materials made of metal oxide and polytorganophosphazenel components is described. The main problem focused on during this research was to avoid phase separation in order to get homogeneous materials. This problem was pursued looking at the formation of genuine chemical bonds between the exploited polyphosphazenes and the inorganic composite networks. Investigations on the thermal, mechanical, and electroconductive properties of the synthesized, phosphazene-containing composite materials showed that these matrices presented improved mechanical and thermal features with respect to those of the original phosphazene macromolecule, while the ionic conductivities of the prepared molecular hybrids doped with lithium or silver trillate are of the same order of magnitude as those measured for the neat, original phosphazene substrate.Presented at the Ist Italian Workshop on Cyclo- and Polytphosphazenel Materials. February 15–16, 1996. at the CNR Research Area in Padova, Italy.     

Synthesis and characterization of low content of different SiO2 materials composite poly (vinylidene fluoride) ultrafiltration membranes

A comparison of the morphology and performance of virgin poly (vinylidene fluoride) (PVDF) ultrafiltration (UF) membrane, and PVDF-composite membranes with low content of two different SiO₂ (N-SiO₂ and M-SiO₂ particles) was carried out. Cross-sectional area and surface morphology of the membranes were observed by scanning electron microscopy and atomic force microscopy. Surface hydrophilicity of the porous membranes was determined through the measurement of a contact angle. Performance tests were conducted on the composite membranes through water flux and bovine serum albumin (BSA) retention. Average pore size and surface porosity were calculated based on the permeate flux. Thermal stability and mechanical stability were determined by thermogravimetric analysis and tensile stress tests. The results indicate that N-SiO₂/PVDF (P-N) membranes possessed larger average pore size and porosity, which led to higher water flux and a slight decline in BSA retention. On the other hand, M-SiO₂/PVDF (P-M) membranes had better mechanical stability and anti-fouling performance with enhanced membrane hydrophilicity and decreased membrane surface roughness. Both of the P-N and P-M membranes exhibited typical asymmetric morphology and improved thermal stability.     

Amine functionalization of poly(styryl)lithium with N-(benzylidene)trimethylsilylamine

Functionalization reactions of poly(styryl)lithium with N-(benzylidene)-trimethylsilylamine produce polymers containing significant amounts of coupling products for M_n = 2.8 × 10³g/mol (19% coupling) and M_n = 15 × 10³g/mol (15% coupling). Isolation and characterization of the products for the amination of poly(styryl)lithium with M_n = 2.8 × 1³g/mol indicates that the non-coupled products consist of a primary amine-terminated polymer (69% yield) and an acetophenone-type functionalized polymer (12% yield). The dimeric product (19% yield) has a primary amine functional group. The formation of these products is rationalized by a Cannizzaro-type reaction of the initially formed polymeric lithium silylamide product with excess N-(benzylidene)(trimethylsilylamine to form the corresponding polymer with imine chain-end functionality which can react with another molecule of poly(styryl)lithium to form dimer product or hydrolyze to the acetophenone functionality on work-up.     

Temperature-dependent interaction parameters of poly(methyl methacrylate)/poly(2-vinyl pyridine) and poly(methyl methacrylate)/poly(4-vinyl pyridine) pairs

Temperature-dependent interaction parameters (α) of poly(methyl methacrylate)/poly(2-vinyl pyridine) (PMMA/P2VP) pair and PMMA/poly(4-vinyl pyridine) (PMMA/P4VP) pair were obtained from the SAXS profiles at various temperatures, and curve fitting to the random phase approximation theory. For this purpose, symmetric P2VP-block-PMMA and P4VP-block-PMMA copolymers were synthesized anionically. The molecular weights of both block copolymers were controlled to exhibit the disordered state over the entire experimental temperatures. We found that the value of α for PMMA/P4VP was larger than PMMA/P2VP, similar to polystyrene (PS)/poly(vinyl pyridine) pairs. However, the difference between in α between PMMA/P2VP and PMMA/P4VP was much smaller than that between PS/P2VP and PS/P4VP. This might be attributed to the hydrophilic PMMA block compared with hydrophobic PS block. Finally, the order-to-disorder transition temperature for symmetric P2VP-block-PMMA copolymers was determined by small angle X-ray scattering and birefringence methods.     

Development of high‐modulus thermoset materials based on bioglycerol

A high‐value application of crude bioglycerol in polymers was developed. In this application, bioglycerol was first transformed into a highly polyunsaturated resin (MAGLYMA) through maleinization–methacrylation reactions, under mild conditions (80–90 °C, 1–2 h). The resin was copolymerized with methyl methacrylate (MMA) (20%–50%) at room temperature over 8 h, affording rigid materials. The effect of MMA content on the mechanical and thermal properties was evaluated. The flexural modulus, flexural strength and surface hardness of the materials were around 3800 MPa, 130–180 MPa and 77 (Shore D), respectively. T_g values were in the range 92–105 °C. It is remarkable that excellent mechanical and thermal properties were obtained using a low concentration of MMA (20%). In particular, the mechanical properties of this material were better than those obtained for a commercial unsaturated polyester thermoset. © 2019 Society of Chemical Industry     

Bioartificial materials based on blends of collagen and poly(acrylic acid)

The interactions between soluble collagen (C) from calf skin and poly(acrylic acid) (PAA) were studied. Mixing aqueous solutions of collagen and PAA, at various pH values (2.5–4), leads to the formation of complexes that precipitate in the form of insoluble aggregates. The effects of mixture composition, pH, and ionic strength on C/PAA complex formation were investigated by gravimetric, turbidimetric, and conductometric analysis. The experimental results indicate that the complexes form through electrostatic interactions. Homogeneous solid films with variable C/PAA ratios were obtained by casting from solutions in which the pH was adjusted just over the isoelectric point of collagen, thus avoiding the attractive ionic interactions responsible for the complexation of collagen and PAA molecules. A relevant result obtained is related to the possibility of restoring the ionic interactions between the two polymers inside the solid films. Mixture composition and pH appear to influence the thermal properties of both complexes and films. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 971–976, 1999