Internal stress of epoxide resin modified with spiro ortho-ester type resin

Bisphenol-A type epoxide resin modified with various amounts of spiro ortho-ester (SOE) resin was cured with an imidazole. Internal stress of the modified systems decreased with increasing fraction of SOE resin in the cured resins. In particular, a drastic reduction of the internal stress was observed in the systems modified with more than 33 mol% SOE resin. In addition, heterogeneous structure was observed with modifier content over 33 mol%, and the elastic modulus of these systems decreased step-wise with increasing ambient temperature. On the other hand, the systems in which the modifier content was less than 20 mol% had homogeneous structure and thus the modulus was considerably higher than that of the former systems. Consequently, it was concluded that the drastic reduction of the internal stress in the systems modified with more than 33 mol% SOE resin depends on the low elastic modulus caused by the formation of heterogeneous structure.     

An emerging technology to cure fiber-reinforced composites: Electron curing

Electron accelerators are being widely used in industry to process polymeric materials. Their use to cure fiber-reinforced composites is an emerging technology, based on the work done here in Canada, and in France. The advantages of electron curing include ambient temperature curing with reduced internal stress, reduced curing times, and overall cost of savings. In this paper we present a brief review of our work with emphasis on the effects of dose and dose rate, temperature rise during curing, internal stress, voids, properties of matrix resins and a comparison of the properties of electron cured and thermally cured matrices and composites.Abbreviations: kW kilo-watt - eV electron volt - RTM resin transfer molding - SEC size exclusion chromatography - Gy Gray (1 Gy = 100 rad) - THF tetrahydrofuran - AMU atomic mass unit - T _g glass transition temperature     

High-pressure autoclave curing for a thermoset composite: effect on the glass transition temperature

The effect of high-pressure curing within an autoclave on the cured glass transition temperature (T _g) of a thermoset fibre-reinforced composite has been studied. The results indicate that an increase in the T _g value was obtained by a higher curing pressure as well as a lower moisture content. Both results have been related to the reduction in the microscopic free volume and the macroscopic void content of the matrix resin. Using the results obtained, the T _g increase was related to the applied autoclave pressure through equations based on both free-volume and thermodynamic concepts, with the results indicating a significantly higher effect than for homogeneous polymers. This has been attributed to a moisture-dominant diffusion process which has been used to explain the growth and reduction of voids.     

Internal stress of epoxy resin modified with acrylic polymers having crosslinks produced byin situ UV radiation polymerization

In order to reduce the internal stress of cured epoxy resin generated by shrinkage in the cooling process from cure temperature to room temperature, two kinds of acrylic polymers were introduced byin situ UV radiation polymerization prior to curing. Polybutyl acrylate (A) and butyl acrylate-monoethylene glycol dimethacrylate copolymer (molar ratio 955) (B) were used as the acrylic polymer. In the A-modified resin, a heterogeneous structure with spherical submicrometre domains were formed. In the B-modified resin, irregularly shaped submicrometre domains in which the microphase separation occurred were observed. The modulus of cured epoxy resin decreased as a result of the modifications, and was lower in the B-modified resin than in the A-modified resin. Therefore the internal stress decreased more effectively in the B-modified resin.     

Temperature dependence of fracture toughness of epoxy resins cured with diamines

The fracture toughness (critical stress intensity factor, K _Ic) of epoxy resins cured with four diamines has been measured as a function of temperature over the range from –35° C to above T _g. It was found that K _Ic for each epoxy-diamine system did not vary below room temperature, and in the higher temperature range K _Ic increased with increasing temperature to a maximum and then decreased. The temperature which maximized K _Ic, agreed with the temperature at which the flexural modulus of the epoxy resins abruptly dropped. This temperature was therefore considered as T _g. This temperature was found to be about 20° C lower than the heat deflection temperature under load (1.82 M Pa) of the resins.     

Miscibility, morphology and fracture toughness of tetrafunctional epoxy resin/poly (styrene-co-acrylonitrile) blends

Poly(styrene-co-acrylonitrile) (SAN) was found to be miscible with the tetraglycidylether of 4,4'-diaminodiphenylmethane (TGDDM), as shown by the existence of a single glass transition temperature (T _g) over the whole composition range. However, SAN was found to be immiscible with the 4,4-diaminodiphenylmethane (DDM)-cured TGDDM. Dynamic mechanical analysis (DMA) shows that the DDM-cured TGDDM/SAN blends have two T _gs. A scanning electron microscopy (SEM) study revealed that all the DDM-cured TGDDM/SAN blends have a two-phase structure. The fracture toughness K _IC of the blends increased with SAN content and showed a maximum at 10 wt% SAN content, followed by a dramatic decrease for the cured blends containing 15 wt% SAN or more. The SEM investigation of the K _IC fracture surfaces indicated that the toughening effect of the SAN-modified epoxy resin was greatly dependent on the morphological structures.     

Thermal rejuvenation in metallic glasses

Abstract

Structural rejuvenation in metallic glasses by a thermal process (i.e. through recovery annealing) was investigated experimentally and theoretically for various alloy compositions. An increase in the potential energy, a decrease in the density, and a change in the local structure as well as mechanical softening were observed after thermal rejuvenation. Two parameters, one related to the annealing temperature, T_a/T_g, and the other related to the cooling rate during the recovery annealing process, V_c/V_i, were proposed to evaluate the rejuvenation phenomena. A rejuvenation map was constructed using these two parameters. Since the thermal history of metallic glasses is reset above 1.2T_g, accompanied by a change in the local structure, it is essential that the condition of T_a/T_g ≥ 1.2 is satisfied during annealing. The glassy structure transforms into a more disordered state with the decomposition of icosahedral short-range order within this temperature range. Therefore, a new glassy structure (rejuvenation) depending on the subsequent quenching rate is generated. Partial rejuvenation also occurs in a Zr₅₅Al₁₀Ni₅Cu₃₀ bulk metallic glass when annealing is performed at a low temperature (T_a/T_g ~ 1.07) followed by rapid cooling. This behavior probably originates from disordering in the weakly bonded (loosely packed) region. This study provides a novel approach to improving the mechanical properties of metallic glasses by controlling their glassy structure.     

Effect of CO2 fixation reaction on the thermal and dynamic mechanical properties of tetrafunctional epoxy resin

A tetrafunctional epoxy resin was modified using CO₂ fixation process in the presence of tetra-n-butyl ammonium bromide as catalyst. The unmodified tetrafunctional epoxy resin (UMTE) and CO₂ fixated modified tetrafunctional epoxy resin (CFMTE) were cured by diethylenetriamine. A bifunctional glycidyl ether compound was used as a reactive diluent to control the viscosity of CFMTE. The activation energy of curing reaction was computed using the advanced integral isoconversional method. The activation energy, which depends on the conversion, was considerably changed due to the CO₂ fixation process. The thermal stability parameters including the initial degradation temperature, the temperature at the maximum rate of weight loss (T _max), and the decomposition activation energy (E _d) were determined by thermal gravimetry. Dynamic mechanical thermal analysis measurements showed that the CO₂ fixation decreases the T _g of the epoxy resin. The surface morphology of UMTE and CFMTE were determined by scanning electron microscope. It is concluded that CO₂ fixation reaction improves the properties of tetrafunctional epoxy resin.     

Poly(ether ether ketone) with pendent methyl groups as a toughening agent for amine cured DGEBA epoxy resin

A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin was modified with poly(ether ether ketone) with pendent methyl groups (PEEKM). PEEKM was synthesised from methyl hydroquinone and 4,4′-difluorobenzophenone and characterised. Blends of epoxy resin and PEEKM were prepared by melt blending. The blends were transparent in the uncured state and gave single composition dependent T _g. The T _g-composition behaviour of the uncured blends has been studied using Gordon–Taylor, Kelley–Bueche and Fox equations. The scanning electron micrographs of extracted fracture surfaces revealed that reaction induced phase separation occurred in the blends. Cocontinuous morphology was obtained in blends containing 15 phr PEEKM. Two glass transition peaks corresponding to epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum of the blends. The crosslink density of the blends calculated from dynamic mechanical analysis was less than that of unmodified epoxy resin. The tensile strength, flexural strength and modulus were comparable to that of the unmodified epoxy resin. It was found from fracture toughness measurements that PEEKM is an effective toughener for DDS cured epoxy resin. Fifteen phr PEEKM having cocontinuous morphology exhibited maximum increase in fracture toughness. The increase in fracture toughness was due to crack path deflection, crack pinning, crack bridging by dispersed PEEKM and local plastic deformation of the matrix. The exceptional increase in fracture toughness of 15 phr blend was attributed to the cocontinuous morphology of the blend. Finally it was observed that the thermal stability of epoxy resin was not affected by the addition of PEEKM.     

Impact-modified epoxy resin with glassy second component

A resorcinol-based epoxy resin was modified by incorporating a glassy second component. The mixture showed a heterogeneous morphology with two clearly defined phases, one phase rich in oligomer, the other phase composed mainly of resorcinol epoxy resin. The fracture toughness measured asG _1c andK _1c values showed an increase from 174J m^–2 and 0.89 MN m^–1.5 S in pure epoxy resin to 431 J m^–2 and 1.36 MN m^–1.5 in 30% oligomer modified resins. The scanning electron micrographs showed that the oligomer-rich phase exhibited ductile failure behaviour and formed the dispersed phase at low concentrations while it was the continuous matrix when the concentration was 30%. Optical observations on the failure mode of thin films of the oligomer-modified epoxy resin showed the existence of both inter face failure and considerable distortion in both phase.     

Influence of post-curing and temperature effects on bulk density,glass transition and stress-strain behaviour of imidazole-cured epoxy network

The effects of post-curing and temperature on the glass transition, bulk density and stress-strain behaviour in the glassy and rubbery state of 2-ethyl-4-methyl imidazole-cured epoxy network have been evaluated by differential scanning calorimetry (DSC), water displacement and tensile testing. The glass transition temperature,T _g, was found to increase with increasing post-cure temperature and the size of the base line shift in the glass transition region on the DSC thermogram can serve as an indicator of the extent of cure. At room temperature, the decrease in bulk density with increasing extent of cure may be attributed to the additional cross-linking, adding molecular constraints to the thermal constraints. Thus, a higher free volume atT _g can be expected to remain in the glassy state as the sample is slowly cooled through the glass transition temperature. In the investigation on the temperature dependence of the tensile mechanical properties, a fracture envelope was obtained. The tensile strength, Young's modulus and ultimate elongation in the glassy and rubbery state are discussed in detail.     

Synthesis and mechanical properties of cardanol-formaldehyde (CF) resins and CF-poly(methylmethacrylate) semi-interpenetrating polymer networks

Cardanol-formaldehyde (CF) resins (both novolac and resol) and CF-poly(methylmethacrylate) (PMMA) semi-interpenetrating polymer networks were synthesized and their mechanical properties and thermal transitions were evaluated. The lower tensile strength of CF resins compared to phenol-formaldehyde (PF) resins may be understood on the basis of the structure of the C₁₅ side chain imparting steric hindrance and reduction in intermolecular interactions. Interpenetration of CF with PMMA increased the mechanical properties only marginally. Scanning electron micrographs of the semi-IPNs showed two distinct phases. Thermomechanical analysis gave two glass transition temperatures,T _g, for the IPNs, the lowerT _g corresponding to the PMMA phase and the higherT _g to the CF phase. However, the unusual increase inT _g of the CF from 128°C to 144°C suggests restrictions in the segmental motion of the CF phase brought about by mixing with another rigid polymer such as PMMA.     

Modification of bifunctional epoxy resin using CO2 fixation process and nanoclay

A bifunctional epoxy resin was modified by using a CO₂ fixation solution process in the presence of tetra n-butyl ammonium bromide (TBAB) as catalyst and the modified treated resin was treated by cloisite 30B as nano additive. The Unmodified epoxy resin (UME), CO₂ fixated modified epoxy resin (CFME), and CFME/clay nano composite (CFMEN), were cured by diethylenetriamine (DETA). A cycloaliphatic compound as a reactive diluent was used to control the viscosity of high viscose CFME. The exfoliation of organoclay in UME and CFME was investigated by X-ray diffraction and activation energy was computed using the advanced integral isoconversional method. The activation energy dependency demonstrated that the mechanism of UME curing did not change in the presence of nanoclay. In contrast, the CO₂ fixation results showed a significant change in the activation energy dependency. The Thermal stability parameters include the initial degradation temperature (IDT), the temperature at the maximum rate of weight loss (T_max), and the decomposition activation energy (E_d) were determined by thermal gravimetry analysis. Dynamic mechanical thermal analysis measurements showed that the presence of organoclay in CFME increases the T_g of nano composite in contrast to UME. The fracture roughness of UME, CFME and CFNE were determined by scanning electron microscope. The exfoliated UME/1%clay nanocomposite was confirmed by TEM image.     

Effect of treated filler loading on the photopolymerization inhibition and shrinkage of a dimethacrylate matrix

This study shows how treated filler loading influences the photopolymerization of a dimethacrylate comonomer mixture, regarding, in particular, shrinkage and inhibition under atmospheric oxygen, present in oral environment. Bis-GMA/TEGDMA (75/25 wt.%) resins were loaded with hybrid filler (Ba aluminosilicate glass and pyrogenic silica), treated with γ-methacryloxy(propyl)trimethoxysilane, at 0–50 wt.% and light cured over a total of 30 s (45 mW/cm²). Degree of double-bond conversion (DC), obtained using FTIR, decreased with filler content. ¹H MAS spectra (293–340 K) and STRAFI images (293 K) were obtained as a function of irradiation time and filler concentration. ¹H signals of unreacted methacrylate groups were more intense for higher loaded resins and resonances from –CH₂SiO₂(OH) (T²) and –CH₂SiO₃– (T³) units, also observed by ²⁹Si NMR, were resolved and suggest the presence of T²–resin bonds. 1D images show a reduction on polymerization contraction and reaction inhibition at the composite resin surface with filler loading. 2D resin images present a highly mobile surface layer, hence with lower DC.     

Moisture absorption by cyanate ester modified epoxy resin matrices. Part V: effect of resin structure

A series of epoxy resins of varying functionality (in terms of the number of epoxide groups) were used to cure the cyanate ester resin, AroCy L10 (1,1-bis(4-cyanatophenyl) ethane). The effect of thermal spiking on moisture absorption and changes in glass transition temperature (T_g) were studied.With the tetra functional (MY720) epoxy a more polar crosslinked density matrix forms. However, after thermal spiking to 140 °C a second peak appeared in the DMTA spectrum which was attributed to partial hydrolysis. The other two systems were much more stable.All systems exhibited the enhancement of moisture absorption as a result of thermal spiking.The mechanism of this phenomenon has been discussed in detail and related to the distribution of unoccupied volume in the dry resin and the location of water molecules at hydrogen bonding sites. The redistribution of the water molecules throughout the sites during thermal cycling is considered responsible for the enhancement and the reduction in moisture contents at high thermal spike temperatures.     

Effects of 3D structure of silsesquioxane moieties on the thermal and optical properties of transparent epoxy/silsesquioxane hybrid materials

Transparent and colorless epoxy/silsesquioxane (SQ) hybrids were prepared by modifying bisphenol-A epoxy resin with two SQ type epoxy resins having different 3D structures, that is, double-decker SQ and cage SQ type epoxy resins. To compare these two hybrids, the cured resin modified with the imperfect ladder SQ epoxy resin was also prepared. The effects of the 3D-structure of the SQ moieties on the thermomechanical, optical and dielectric properties of the cured epoxy/SQ hybrids were investigated. Thus, the refractive index and dielectric constant of the hybrids significantly decreased with an increase in the contents of the SQ moieties. This is due to the introduction of Si atoms with a low atomic polarity and large intermolecular space that was estimated from the difference between the volume of the space surrounded by “Connolly surface” and the van der Waals volume of the SQ moieties. The glass transition temperature, T _g, also decreased with the introduction of the SQ moieties, due to the increase in the intermolecular space. Thus, it was concluded that the performance of the epoxy/SQ hybrids depends not only on the SiO_3/2 content, but also on the 3D structure of the SQ moieties.     

Thermal and dynamic mechanical properties of IPNS formed from unsaturated polyester resin and epoxy polyester

The interpenetrating polymer networks (IPNs) were formed by unsaturated polyester resin (UPR) polymerized by free radical initiators: benzoyl peroxide (BPO) or cumene hydroperoxide (CHP) and epoxy polyester (EP), cured with acid anhydrides: tetrahydrophthalic anhydride (THPA) or maleic anhydride (MA). IPNs consisting 10, 30, 50, 70, 90 wt% of EP were prepared. The effect of the EP component in the IPNs and the type of curing agent on the cure behavior, thermal, and viscoelastic properties have been investigated. The results showed that both EP content and used curing system influenced on studied properties. As the EP content increased, the glass transition temperatures (T _g) also increased. Moreover, higher values of tanδ_max and lower values of cross-linking density in a rubbery state (ν_e) of IPNs containing higher EP content, probably due to plasticization effect of EP component were observed. Additionally, more heterogeneous network structure (higher values of the full-width at half-maximum (FWHM) as the EP content decreased was prepared. The thermal and viscoelastic properties of the blends cured with BPO/MA or CHP/MA system were considerably better than those cured with BPO/THPA or CHP/THPA. The higher stiffness, ν_e, T _g and lower tanδ_max values were obtained. It was probably connected with the interactions of carbon–carbon double bonds of MA with vinyl monomer (styrene), UPR and radical initiators causing to obtain more cross-linked polymer network structure. This supposition was confirmed on basis of the cure reaction monitored by DSC. The chemical interactions between two components of the blends and epoxy hardener caused that the BPO/MA or CHP/MA cure systems influenced on the cure behavior of UPR and EP components in the IPNs. The exotherm peak temperature (T _max1) shifted to lower values compared to these in the neat UPR whilst T _max2 shifted to higher values than in the neat EP. However, the cure behavior of the UPR was not greatly affected by the presence of EP component when BPO/THPA or CHP/THPA cure systems were used due to the lack of chemical interactions between the components and their curatives.     

加成型酚醛改性双马树脂及其复合材料性能

双马来酰亚胺(BMI)树脂因其优异的性能已在航空航天、电子和其他工业领域获得应用,为满足其在高速飞行器结构件中需求,用加成型酚醛树脂改性BMI体系以改善其热-力学性能。通过Williamson醚化反应合成了炔丙基醚化酚醛树脂(PN)和烯丙基醚化酚醛树脂(AN),采用熔融共混法分别与N,N’-(4,4’-亚甲基二苯基)双马来酰亚胺(BDM)和2,2’-二烯丙基双酚A(DABPA)树脂体系(BD)共混,制备了三元热固性树脂：PN改性BD(BDPN)和AN改性BD(BDAN)。研究了两种加成型酚醛树脂改性的BD树脂体系的加工工艺性和固化行为的变化,并对改性前后固化树脂及其复合材料的热、力学性能进行了研究。结果表明：共混树脂体系都在极性溶剂中有好的溶解性,加工窗口都有50℃以上。BDPN和BDAN固化反应只有一个放热峰,最高放热峰值温度比BD树脂低。用FTIR跟踪验证了BD、BDPN和BDAN树脂体系发生的Ene、DielsAlder、Claisen重排和炔基与马来酰亚胺环的聚合反应。PN热氧稳定性好,改性的BDPN固化树脂空气中质量损失5wt%的温度(T_d5)高于400...     

The β-relaxation in epoxy resins; the temperature and time-dependence of cure

Internal friction and creep measurements have been used to reveal the mechanism of cure in epoxy resins cross-linked with diethylene triamine (DETA). The -relaxation is associated with the main glass transition of the undercured resin network. The glass transition temperature (T _g) is about 40° C above the maximum temperature of cure and the curing reaction slows down about 2 h after each increase of the temperature. At 25° C the cure is only about half complete and since in this resin, when fully cross-linked, T _g is at about 140° C, temperatures of 100° C or over are needed to complete cure.