Cure kinetics and thermomechanical properties of thermally stable photopolymerized dimethacrylates

A range of dimethacrylates with varying backbone flexibility were partially photocured to various conversions using p‐xylylene bis‐(N,N‐diethyldithiocarbamate) as a photoiniferter and their glass transition region investigated by dynamic mechanical thermal analysis. For isothermally cured samples, the final degree of conversion was found to increase as the length of the spacer group in the monomer was increased or as the crosslink density in the resin was lowered due to the reduced glass transition temperature which allowed greater mobility and, hence, higher cure. Increasing the curing temperature also resulted in a higher degree of conversion as the network was able to polymerize further before vitrification occurred. For the partially photocured samples, the glass transition temperature was raised as the degree of conversion was increased. Most of the measures of the breadth of the glass transition were found to increase with increased conversion for dimethacrylates with short or stiff backbones (TETDMA and bisGMA) while the transition breadth was independent of conversion for either a more flexible dimethacrylate (NEGDMA) or a dimethacrylate network with a lower crosslink density (50 wt % bisGMA/50 wt % PGEMA). This conclusion was generally confirmed by analysis of the viscoelastic parameters in the frequency domain. It is not clear whether these behaviors resulted from differences in the range of molecular motions available in tight networks or if they were due to spatially heterogeneous regions in the network. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3753–3766, 2003     

Preparation and properties of octadecylamine modified graphene oxide/styrene‐butadiene rubber composites through an improved melt compounding method

Octadecylamine modified graphene oxide/styrene‐butadiene rubber (GO‐ODA/SBR) composites are prepared by a novel and environmental‐friendly method called “Improved melt compounding”. A GO‐ODA/ethanol paste mixture is prepared firstly, and then blended with SBR by melt compounding. GO‐ODA sheets are uniformly dispersed in SBR as confirmed by scanning electron microscope, transmission electron microscopy, and X‐ray diffraction. The interfacial interaction between GO‐ODA and SBR is weaker than that between GO and SBR, which is proved by equilibrium swelling test and dynamic mechanical analysis. GO‐ODA/SBR show more pronounced “Payne effect” than GO/SBR composites, indicating enhanced filler networks resulted from the modification of GO with ODA. GO‐ODA/SBR composite has higher tensile strength and elongation at break than SBR and GO/SBR composite. The tensile strength and elongation at break for the composite with 5 parts GO‐ODA per hundred parts of rubber increase by 208% and 172% versus neat SBR, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42907.     

Thermal and mechanical properties of liquid silicone rubber composites filled with functionalized graphene oxide

To improve the thermal and mechanical properties of liquid silicone rubber (LSR) for application, the graphene oxide (GO) was proposed to reinforce the LSR. The GO was functionalized with triethoxyvinylsilane (TEVS) by dehydration reaction to improve the dispersion and compatibility in the matrix. The structure of the functionalized graphene oxide (TEVS‐GO) was evaluated by Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD), and energy dispersive X‐ray spectroscopy (EDX). It was found that the TEVS was successfully grafted on the surface of GO. The TEVS‐GO/LSR composites were prepared via in situ polymerization. The structure of the composites was verified by FTIR, XRD, and scanning electron microscopy (SEM). The thermal properties of the composites were characterized by TGA and thermal conductivity. The results showed that the 10% weight loss temperature (T₁₀) increased 16.0°C with only 0.3 wt % addition of TEVS‐GO and the thermal conductivity possessed a two‐fold increase, compared to the pure LSR. Furthermore, the mechanical properties were studied and results revealed that the TEVS‐GO/LSR composites with 0.3 wt % TEVS‐GO displayed a 2.3‐fold increase in tensile strength, a 2.79‐fold enhancement in tear strength, and a 1.97‐fold reinforcement in shear strength compared with the neat LSR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42582.     

Mechanical properties and dynamic mechanical analysis of thermoplastic‐natural‐rubber‐reinforced short carbon fiber and kenaf fiber hybrid composites

The hybridization of thermoplastic natural rubber based on carbon fiber (CF) and kenaf fiber (KF) was investigated for its mechanical and thermal properties. Hybrid composites were fabricated with a melt‐blending method in an internal mixer. Samples with overall fiber contents of 5, 10, 15, and 20 vol % were subjected to flexural testing, and samples with up to 30% fiber content were subjected to impact testing. For flexural testing, generally, the strength and modulus increased up to 15 vol % and then declined. However, for impact testing, higher fiber contents resulted in an increment in strength in both treated and untreated composites. Thermal analysis was carried out by means of dynamic mechanical analysis on composites with 15 vol % fiber content with fractions of CF to KF of 100/0, 70/30, 50/50, 30/70, and 0/100. Generally, the storage modulus, loss modulus, and tan δ for the untreated hybrid composite were more consistent and better than those of the treated hybrid composites. The glass‐transition temperature of the treated hybrid composite was slightly lower than that of the untreated composite, which indicated poor damping properties. A scanning electron micrograph of the fracture surface of the treated hybrid composite gave insight into the damping characteristics. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development of high Tg epoxy resin and mechanical properties of its fiber‐reinforced composites

A new epoxy resin with high glass transition temperature (T_g) (～ 180°C) and a viscosity low enough for infiltration into dry reinforcements at 40°C was developed for the vacuum‐assisted resin transfer molding process. To study the curing behavior and viscosity, several blends were formulated using multifunctional resin, aromatic hardener, and reactive diluents. Effects of these components on the viscosity and T_g were investigated by thermomechanical analysis, dynamic scanning calorimetry, and rheometer. Experimental results showed that a liquid aromatic hardener and multifunctional epoxy resin should be used to decrease the viscosity to <1 Pa·s at 40°C. Moreover, the addition of a proper reactive diluent decreased the viscosity and simultaneously minimized the deterioration of T_g. Mechanical properties of the composite produced with the optimized blend were evaluated at both room‐temperature and high‐temperature conditions. According to the results, the composite showed comparable mechanical properties with that of the current commercial resin. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Confinement effects at nanoscale in natural rubber composites: Influence on macroscopic properties

The study of molecular level interactions in elastomer composites has got very scant attention even though a large number of studies are going on in this topic. This work embodies the understanding of confinement effects in natural rubber (NR)/ ZnO composites from micro to nano length scales, and their influence on macroscopic properties of the composites. The interactions between fillers and matrix are characterized from the Donth's approach, which allows estimating the cooperativity size N_α at the glass transition, N_α being directly related to the filler-matrix interactions. The improved properties of NR-nano ZnO composites can be attributed to microstructural and morphological changes due to nano ZnO in the NR matrix. A correlation between N_α, the constrained volume C_v and the thickness of immobilized polymer chains χ_m at the glass transition has also been established. Thus, this work proves that the Donth's approach is a powerful probe to estimate the enhance of mechanical properties in nanocomposites from calorimetric investigations.     

Structure and mechanical properties of polysulfone‐based in situ composites

Composites based on the polysulfone of bisfenol A (PSF) and a liquid‐crystalline copolyester (Rodrun 5000) were obtained by two processing methods, (1) direct injection moulding (DI) and (2) extrusion followed by injection moulding (PI), across the whole composition range. The blends were immiscible and showed two pure amorphous phases. The inferior mechanical properties of PI blends, and their more difficult processing, meant that the PI procedure is not suitable in these blends. The generally linear relationship of the Young's modulus of the DI blends is due to the counteracting effects of the large orientation of the skin and its low thickness. The improvement in notched impact strength of PSF on the addition of small amounts of LCP indicated an important reduction in its notch sensibility. The tensile strength behaviour was close to linearity, with the exception of the 20/80 blend in which it was synergistic. This had been seen in previous thermoplastic/LCP blends, and depicts a behaviour reminiscent of rubber‐toughened blends. Copyright © 2004 Society of Chemical Industry     

Polymeric seal degradation in nuclear power plants: Determination of physical and mechanical properties

To assess the suitability of different materials as polymeric seals in the Nuclear Industry three commercial samples of nitrile rubber at grades BA40, BA50, and BA60 have been tested. Differential scanning calorimetry was used to find the glass transition temperature (T_g) and a Lloyds Texture Analyser 500 (TA500) was used to find the ratio of energy returned during relaxation against energy applied during compression. The mechanical properties determined from these experiments were then compared against the materials infrared spectra to infer structural characteristics. These were in turn cross‐analyzed against the materials ability to swell in a liquid solvent and absorption behavior in a gaseous solvent. From this information, a statement could be made about each material's capacity to perform as a seal. It was thus found that the high energy retention and low absorption characteristics of BA40 made this material the best choice out of those studied for use as a polymeric seal in the nuclear industry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45814.     

Dynamic mechanical properties of three‐component composites (acrylic polymer/epoxy/SiO2) in the glass‐transition region

In previous studies, we reported the linear and nonlinear rheological properties of three‐component composites consisting of acrylic polymer (AP), epoxy resin (EP), and various SiO₂ contents (AP/EP/SiO₂) in the molten state. In this study, the dynamic mechanical properties of AP/EP/SiO₂ composites with different particle sizes (0.5 and 8 μm) were investigated in the glass‐transition region. The EP consisted of three kinds of EP components. The α relaxation due to the glass transition shifted to a higher temperature with an increase in the volume fraction (?) for the AP/EP/SiO₂ composites having a particle size of 0.5 μm, but the α relaxation scarcely shifted for the composite having a particle size of 8 μm as a general result. This result suggested that the SiO₂ nanoparticles that were 0.5 μm in size adsorbed a lot of the low‐glass‐transition‐temperature (T_g) component because of their large surface area. The AP/SiO₂ composites did not exhibit a shift in T_g; this indicated that the composite did not adsorb any component. The modulus in the glassy state (E′_g) exhibited a very weak &phis; dependence for the AP/EP/SiO₂ composites having particle sizes of 0.5 and 8 μm, although E′_g of the AP/SiO₂ composites increased with &phis;. The AP/EP/SiO₂ composites exhibited a peculiar dynamic mechanical behavior, although the AP/SiO₂ composites showed the behavior of general two‐component composites. Scanning electron microscopic observations indicated that some components in the EP were adsorbed on the surface of the SiO₂ particles. We concluded that the peculiar behavior of the AP/EP/SiO₂ composites was due to the selective adsorption of the EP component. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40409.     

Effects of hygrothermal aging on the thermomechanical properties of a carbon fiber reinforced epoxy sheet molding compound: An experimental research

Carbon fiber sheet molding compounds (C-SMCs) are discontinuous fiber reinforced composite materials. Among them, epoxy-based C-SMCs are becoming relevant materials due to their high thermomechanical performance and better formability than continuous fiber reinforced composites. The thermomechanical performance of epoxy resins and epoxy based continuous carbon fiber composites have shown to be influenced by hygrothermal aging. In this work, this influence is studied for an epoxy-based C-SMC. Epoxy-based C-SMC samples were hygrothermally aged by means of accelerated conditioning, exposing them to 65% relative humidity, and 80°C in a climatic chamber. The equilibrium moisture content, as well as the moisture diffusion coefficient has been determined. The thermomechanical properties of epoxy C-SMC have been analyzed by dynamic mechanical analysis, tensile, 3-point bending, and short beam tests in dry and aged samples. The results showed that epoxy C-SMC is affected by hygrothermal aging in the cases of moisture intake and its effects on T_g value, but interestingly, the hygrothermal aging did not generate any degradation effects in the mechanical response of epoxy C-SMC.     

Free‐volume effects on the thermomechanical performance of epoxy–SiO2 nanocomposites

In this study, free‐volume effects on the thermal and mechanical properties of epoxy–SiO₂ nanocomposites were investigated. SiO₂ particles ranging from 15 nm to 2 µm were used, and the nature of the matrix–filler interphase was modified by surface grafting. Nanoparticles 15 nm in diameter yielded an increase in the glass‐transition temperature (T_g) of the composites up to 5 °C; at the same time, they increased the storage modulus (E′) from 2340 to 2725 MPa. Conversely, large particles markedly decreased both T_g and E′; this suggested the pivotal role of nanoparticle size on the final properties of the nanocomposite. The functionalization of SiO₂ nanoparticles markedly improved their dispersion within the epoxy matrix. The positron annihilation lifetime spectroscopy results indicate that the free volume strongly depended on the interphase. These experimental findings obtained here could be extrapolated to industrially relevant nanocomposites and could provide a rationale for the comprehension of free‐volume effects on the thermal and mechanical properties of nanocomposite materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45216.     

Effects of four isocyanates and four plasticizers on the thermomechanical and tensile properties of hydroxyl-terminated polybutadiene elastomers and the effect of solid particle filling

The aim of this study is to analyze effect of four different isocyanates and four different plasticizers in hydroxyl-terminated polybutadiene (HTPB) based elastomers by quantitative analysis of the shape of the loss factor (tan δ), tensile strength, deformation frequency shift of the maximum temperatures of loss moduli G" and of tan δ. The first part of the study shows intensities of the tan δ curves with the four isocyanates follow the order HDI > IPDI > H12MDI > Desmodur™ E305. By molecular modeling of the isocyanates and the corresponding polyurethane parts the influence of molecular geometry on tan δ are discussed. The second part of the study analyzes HTPB-IPDI elastomers with the four different plasticizers DOA, DOS, DOZ, and IDP. The IDP provides lowest T_g at about −83°C, while the others provide at about −78°C. In the third part, aluminum (Al-18 μm) and ammonium perchlorate (AP-200 μm) are added to HTPB-IPDI+DOA to analyze the effect of particle size, wt% content and particle type on the shape and intensity of the tan δ curves. From the frequency shift of the two maximum temperatures one receives activation energies Eaf. Their average values without and with plasticizer are with tan δ 178 and 165 kJ/mol and with G" 274 and 248 kJ/mol, respectively.     

Investigation of free volume and damping property for polycarbonate/multiwalled carbon nanotube composites by positron annihilation technology

Microstructure and damping characteristics were investigated for polycarbonate/multiwalled carbon nanotube (PC/MWCNT) composites. Dynamic mechanical analysis results show that the damping factor and the value of the energy loss fraction w are significantly increased. Especially, nearly 300% improvement in damping factor is observed in the temperature range from 140 to 150°C. Positron annihilation lifetime measurements indicate that both the o-Ps lifetime and the free volume increase with increasing MWCNT content, leading to decrease in the glass transition temperature and increase in the damping properties. The relationships among the damping, mechanical property, and the free volume have been first observed, that is, the increase of the free volume brings about a reduction in tensile strength and an increase in damping. The interfacial friction slipping of MWCNTs and the free volume play an important role in determining the damping property of PC/MWCNT composites. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The properties and suitability of commercial bio-based epoxies for use in fiber-reinforced composites

Environmental concerns about fiber composites are leading manufacturers to consider bio-based alternatives to petroleum-derived epoxies. Such a substitution is hindered by a lack of information, so commercially available bio-based epoxy systems have been compared, their mechanical properties measured, and fiber composites produced by vacuum infusion. Most high bio-based content resins for infusion use conventional curing agents. Bio-based content is generally added using Epicerol, but also other bio-based precursors. A diglycidyl ether of bisphenol A system produced using Epicerol achieves 20 % bio-based content, but achieves higher contents when Epicerol is used in diluents. Fully bio-based monomers can be deleterious to the mechanical properties and glass transition temperature (T_g), so are used sparingly. The most-promising systems (28 % to 43 % bio-based) compare well to conventional epoxies, possessing good strength, stiffness, toughness, and a reasonable T_g. These partially bio-based epoxies offer an immediate lower-carbon alternative for vacuum-infused composites in marine, sports equipment, and wind energy.     

Effect of polymer structures on electro-optical properties of polymer stabilized liquid crystal films

The polymer stabilized liquid crystal (PSLC) film is a relatively novel electro-optical material, which is generally obtained by dissolving a small amount of a bifunctional photoreactive monomer in a low molecular mass liquid crystal. In this paper, the PSLC films were prepared with photoreactive biphenyl methacrylate monomers by photopolymerization induced phase separation. The effects of liquid crystal concentration, curing time, monomer structures and alignment layer on the electro-optical properties of PSLC films were investigated. The results show that the transmittance in the OFF state (T _OFF) increased with the liquid crystal concentration, but the driving voltage decreased. T _OFF was also influenced by the curing time. Furthermore, when polyimide was used as alignment layer, the films prepared from the bifunctional monomer shows a higher T _OFF, while those from the single functional monomer exhibited a deformed electro-optical curve due to the unsteady polymer networks. __________ Translated from Polymer Materials Science and Engineering, 2008, 24(1): 63–66 [译自: 高分子材料科学与工程]     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

Morphology and thermal properties of liquid crystal p‐PAEB/styrene copolymer

The homopolymer of unsaturated liquid crystal (LC) monomer for p‐phenylene di {4‐[2‐(allyloxy) ethoxy] benzoate} (p‐PAEB), and copolymer poly (p‐PAEB/St) of p‐PAEB with styrene (St) have been synthesized. The LC behavior and thermal properties of p‐PAEB and poly(p‐PAEB/St) have been studied by Polarizing Optical Microscopic (POM), Differential Scanning Calorimetry, X‐Ray Diffractometer (XRD), and Torsional Braid Analysis (TBA). The results demonstrate that LC phase texture and phase transition temperature of copolymers are affected by the composition of LC units in copolymers. The POM and XRD reveal that p‐PAEB has a smectic phase structure; the copolymer of p‐PAEB with styrene reveal deformed focal conics texture of smectic phase. The phase transition temperature range of p‐PAEB is 120.5–191.5°C, but the homopolymer of p‐PAEB has a broad LC temperature range from 77 to 170°C. The LC temperature range of poly(p‐PAEB/St) is broadened with increased content of p‐PAEB. The dynamic mechanical properties of LC polymer networks were investigated with TBA. The results indicate that the peak temperature of maximal mechanical loss is 114°C and is decreased with the addition of styrene © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5731–5736, 2006     

Transmission and Mechanical Properties of Optical Adhesives

The optical, mechanical and durability performance of selected epoxy, polyester, UV-curable acrylic, cyanoacrylate and silicone adhesives were evaluated and measured for bonding applications of optically transparent glasses in the visible and infra-red regions of the electromagnetic spectra.

From the initially selected adhesives only the UV-curable modified acrylic, two-component silicone and room temperature cured epoxy, were found to be of high performance characteristics, having good transmission properties and enhanced endurance in a combination of heat and humidity and following thermal cycling.

Sodium chloride substrates served as adherends for the transmission characterization of the optical adhesives, due to their high transmission properties in the 0.4-10 m μ spectral range. A modified lap shear specimen was designed for studying the mechanical properties and failure mechanisms of the adhesives and their durability in a humid and not environment. Finally, a two-piece glass doublet was used for investigating the optomechanical characteristics of the optical adhesive following environmental conditioning and thermal shock cycling.

Due to the inherent C-C bond, polymer adhesives are limited in utility, as far as transparency is concerned, close to 3.5 μm and in most of the 8-12 μm spectral range.     

The effect of adding devulcanized rubber on the thermomechanical properties of recycled polypropylene

This work aims to investigate the effect of adding vulcanized or partially devulcanized rubbers on recycled polypropylene (PPr), considering thermomechanical and morphological properties. The study proposes to better understand how structural changes underwent by rubber (after the devulcanization) contributed to improving the mechanical properties of the PPr. The PPr/rubber blends were prepared by a co-rotating twin-screw extruder and then were injected. The blends composed of the most devulcanized rubbers by microwaves with refined microstructure showed higher values of elongation at break and toughness. Data showed that the devulcanization process applied to the rubber interfered positively in its adhesion to the PPr. Data from dynamic mechanical analysis and atomic force microscopy indicated that the most devulcanized rubbers presented an interface more connected to PPr. These chemical interactions possibly impacted the mechanical properties of the PPr. Moreover, dilatation processes favored the fracture mechanisms of the PPr when rubber was added to it.     

Studies of thermal,mechanical properties,and kinetic cure reaction of carboxyl-terminated polybutadiene acrylonitrile liquid rubber with diepoxy octane

Epoxy resins, despite their unique properties, have limitations in many applications due to their low fracture toughness. One of the most effective methods to overcome this limitation is to use toughening agents, such as carboxyl terminated poly butadiene-acrylonitrile (CTBN) in the epoxy matrix. CTBN can react with various compounds, such as epoxies. In this study, we investigated the severity of CTBN sedimentation with di epoxy octane (DEO) in the presence basis catalysts. The studied of the physical properties of the synthesized copolymer in the presence of pyridine compared to other catalysts increases mechanical properties (248.43% elongation, 0.63 MPa strength, and 32 hardness with Shore A) and decreases the glass transition temperature (−45.1) of the copolymer. Investigated the cure kinetics of the CTBN-DEO reaction was in the presence of pyridine using a nonisothermal technique of differential scanning calorimetry, and the curing kinetic parameters, such as activation energy (E_a), pre-exponential factor (A), and rate constant (k), were calculated by different kinetic methods. The obtained curing kinetic values with different kinetic methods are well-matched, the E_a values are in the range of 91.3–97.1 kJ.mol⁻¹ and the A values are in the range of 0.48 × 10¹¹–1.51 × 10¹¹ S⁻¹.