Molecular relaxation phenomena during accelerated weathering of a polyurethane coating

Results from a polyester-urethane (PU) coating system under accelerated weathering showed that crosslink density, obtained from high-temperature modulus data, diminished due to chain scission. However, T _g and room-temperature tensile modulus both increased with weathering. Molecular relaxation phenomena in polymers have long been investigated to explore changes occurring in a polymer at temperatures below its glass transition and were explored for an explanation to supplement chemical degradation for these observations. Relaxation was quantified using “enthalpy recovery” which first increased with exposure, then diminished. The concurrent physical and chemical aging effects were characterized by tracking nonexponentiality in the spectrum of relaxation times, and the size of “co-operatively relaxing regions” deduced from relaxation around the glass transition. Mechanical relaxation in this coating extended longer than cycle periods typical of accelerated weathering, suggesting that frequency effects might be important when comparing accelerated to natural weathering. This paper was awarded Third Place in the John A. Gordon Best Paper competition, presented as part of 2006 FutureCoat! Conference, sponsored by Federation of Societies for Coatings Technology, November 1–3, 2006, in New Orleans, LA.     

The temperature-dependence of some mechanical properties of a cured epoxy resin system

The tensile mechanical properties and fracture toughness of a Bisphenol-A type difunctional epoxy resin, cured with different amounts of metaphenylene diamine, using two cure cycles, were determined over a range of temperature. The tensile modulus in the glassy state was seen to be predominantly related to intermolecular packing, while in the rubbery state crosslink density was the important factor. Yielding appeared to be due to an increase in free volume as a result of dilatation during the tensile test and was related to a critical shear stress. The large strain properties like tensile strength, elongation-to-break, and toughness showed a more complex dependence on chemical structure, molecular architecture, intermolecular packing, and crosslink density. The roles played by the relaxation processes in determining mechanical properties are highlighted.     

Nanoindentation of shape memory polymer networks

This work examines the small-scale deformation and thermally induced recovery behavior of shape memory polymer networks as a function of crosslinking structure. Copolymer shape memory materials based on diethylene glycol dimethacrylate and polyethylene glycol dimethacrylate with a molecular weight of 550 crosslinkers and a tert-butyl acrylate linear chain monomer were synthesized with varying weight percentages of crosslinker from 0 to 100%. Dynamic mechanical analysis is used to acquire the bulk thermomechanical properties of the polymers, including the glass transition temperature and the elastic modulus over a wide temperature range. Instrumented nanoindentation is used to examine ambient temperature deformation of the polymer networks below their glass transition temperature. The glassy modulus of the networks measured using nanoindentation is relatively constant as a function of crosslinking density, and consistent with values extracted from monotonic tensile tests. The ambient temperature hardness of the networks increases with increasing crosslinking density, while the dissipated energy during indentation decreases with increasing crosslinking density. The changes in hardness correlated with the changes in glass transition but not changes in the rubbery modulus, both of which can scale with a change in crosslink density. Temperature induced shape recovery of the indentations is studied using atomic force microscopy. For impressions placed at ambient temperature, the indent shape recovery profile shifts to higher temperatures as crosslink density and glass transition temperature increase.     

Effect of Aging on the Mechanical Properties of UV Curable Optical Fiber Coatings

Abstract

A dual-layer urethane acrylate UV-cured coating is widely used to protect optical fibers because of its well-balanced mechanical properties, weathering resistance and rapid curing. The long-term mechanical behavior of fiber coatings is important for the reliability of optical fibers. Long-term exposure of UV-cured polyether urethane acrylate films was carried out in dry air and in water at elevated temperatures. Tensile testing was performed to reveal changes in mechanical properties and dynamic mechanical analysis to determine both the glass transition temperature and the crosslink density. The equilibrium swelling allowed assessment of the crosslink density. Tensile testing and strip force measurements were performed on virgin and aged optical fibers. Initially the fracture strengths of the secondary coatings increased under all aging conditions indicating post-curing reactions and the possible loss of uncrosslinked species. Aging under wet conditions led at a later stage to hydrolytic degradation of the network and to a decrease in the fracture stress. The equilibrium swelling and equilibrium modulus measurements showed good correlation with the changes in strength. The primary coatings showed a decrease in mechanical strength after only 2–4 weeks under all conditions.     

Dynamic mechanical response of model epoxy networks in the glassy state

The dynamic mechanical properties of model epoxy-amine networks are investigated in the glassy state over a wide range of frequencies, at temperatures between 123 K and 350 K. The effects of crosslink density and network chain flexibility on the β relaxation are examined. Motions responsible for the β process begin to develop at the same temperature, whatever the crosslink density. However, an increase in crosslink density is accompanied by an increase in amplitude and a broadening towards high temperatures of both damping tan δ and loss modulus E″. This effect is responsible for the decrease of elastic modulus E′ at room temperature with increasing crosslink density.     

Xanthate accelerators for low temperature curing of natural rubber

Zinc salts of ethyl, isopropyl, and butyl xanthates were prepared in the laboratory. They were purified by reprecipitation and were characterized by IR, NMR, and thermogravimetric analysis techniques. The melting points were also determined. The rubber compounds with different xanthate accelerators were cured at temperatures from 30 to 150°C. The sheets were molded and properties such as tensile strength, tear strength, crosslink density, elongation at break, and modulus at 300% elongation were evaluated. The properties showed that all three xanthate accelerators are effective for room temperature curing. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1769–1775, 2000     

浇注PBX炸药老化过程中交联密度与力学性能的关系

为分析浇注PBX炸药交联密度与力学性能的关系,在70℃时对浇注PBX炸药样品进行高温加速老化试验,对比分析了平衡溶胀法和核磁共振(NMR)法测定交联密度的差异,研究了其在常温时的抗拉强度(σm)、抗压强度(σb)、压缩率(εb)、抗剪强度(τ)、硬度(SH)与黏结剂母体凝胶分数(G)、交联密度(ve)之间的关系。用动态热机械分析仪(DMA)分析了不同老化时间下样品损耗因子tanδ和黏弹系数的变化规律。结果表明,PBX炸药样品的交联密度在老化初期增加,老化中期略有降低,老化后期又增加;NMR法因其测试简单、快捷,精确度高、试样非破坏性等优点,可以作为今后浇注PBX炸药交联密度表征方法的一个重要发展方向;样品老化过程中,浇注PBX炸药样品的交联密度与各力学性能的变化呈线性相关,其力学损耗降低的原因是黏结剂母体的G和v_e增加,浇注PBX炸药的降解和交联是由黏结剂母体结构变化引起。     

Mechanical and chemical properties of metakaolin-based geopolymer exposed to elevated temperature

A method is presented to fabricate metakaolin-based geopolymers that are structurally and mechanically stable up to 600°C. The chemical environment of the geopolymers is characterized using thermogravimetric analysis and Fourier-transform infrared spectroscopy. Residual free water turned into steam and caused damage to the geopolymer when exposed to elevated temperatures. The curing temperature was increased from 80 to 120°C to remove water during the curing process. A correlation was drawn between the amount of Si-O-Al linkage formed and the position of fingerprint peaks in infrared spectra, providing a tool to evaluate the level of geopolymerization. Flexural and tensile properties of geopolymers fabricated using the optimized method were measured for no heat treatment and for exposure to elevated temperatures of 200, 400, and 600°C. The flexural strength was measured to be 10.80 ± 2.99 MPa at room temperature, 10.36 ± 0.64 MPa at 400°C, and 8.04 ± 1.60 MPa at 600°C. The flexural modulus is reported to be 13.09 ± 3.40 GPa at room temperature and 11.03 ± 0.53 GPa at 600°C. The flexural toughness decreased with increasing temperature. The tensile properties of the geopolymer were measured with direct tensile tests paired with an extensometer. The tensile strength decreased from 4.16 ± 2.08 MPa at room temperature to 3.13 ± 0.97 MPa at 400°C, and 2.75 ± 0.86 MPa at 600°C. The Young's modulus decreased from 45.38 ± 30.30 GPa at room temperature to 26.88 ± 6.65 GPa at 600°C. Both flexural and tensile tests have shown that the metakaolin-based geopolymers cured at 120°C is mechanically stable at temperatures up to 600°C.     

Structure-property relations of polyethertriamine-cured bisphenol-A-diglycidyl ether epoxies

The relations between the chemical and physical network structure, the deformation and failure processes and the tensile mechanical properties of polyethertriamine-cured bisphenol-A-diglycidyl ether epoxies are reported for a series of epoxy glasses prepared from a range of polyethertriamine concentrations. Near-infra-red spectroscopy indicates that these glasses form exclusively from epoxide-amine addition reactions. Their T_g exhibits a maximum and swell ratio a minimum at the highest crosslink density. Stress-birefringence studies reveal that these highly crosslinked glasses are ductile and undergo necking and plastic deformation. The plastic deformation initially occurs homogeneously but ultimately becomes inhomogeneous and shear bands develop. Tensile failure occurs in the high strain shear band region. The ultimate tensile strain of these epoxies attains a maximum of 15% for the highest crosslinked glass. Off stoichiometric networks fail at lower strains because such networks inherently contain more defects in the form of unreacted ends. The density, yield stress, tensile strength, and modulus of these glasses all decrease with increasing polyethertriamine concentration as a result of increasing free volume because of the poor packing ability of the amine molecule. A slight minimum is superimposed on this downtrend in density and modulus with increasing amine content at the highest crosslink density because of geometric constraints imposed on segmental packing by the network crosslinks. The ability of these crosslinked glasses to undergo deformation is discussed in terms of the free volume and the crosslinked network topography. Network failure is considered in terms of stress-induced chain scission which is determined by the concentration ad extensibility of the least extensible network segments.     

拉伸过程中橡胶交联网络结构变化研究

研究拉伸过程中乳聚丁苯橡胶交联网络结构的变化情况.试验结果表明:硫黄用量对交联密度和交联键类型均有影响;微小变形下,利用交联密度通过统计力学理论计算得出的硫化胶模量理论值增量与实测值增量具有较好的一致性;在拉伸过程中,硫化胶总交联密度减小;与转变点(应力-应变曲线拐点)相比,断裂点硫化胶的总交联密度变化不大,但单双硫键交联密度增大,且增量与拉伸初期硫化胶多硫键含量线性相关,说明断裂的部分多硫键重组为单双硫键.     

Thermal aging of bentonite‐filled ethylene propylene diene monomer composites

Bentonite‐filled ethylene propylene diene monomer (EPDM/Bt) composites were prepared using two roll mill compounding method and the effect of Bt loading on the thermal aging, swelling resistance and crosslink density of EPDM/Bt composites were studied. The effect of in situ addition of different silane coupling agents (SCAs) on the above properties at optimum Bt loading of EPDM/Bt composite was also investigated. Thermal aging test results show that the tensile strength and tensile modulus at 100% elongation (M100) increase initially for 2 days aged composites and decrease slightly after 4 days of aging, meanwhile the elongation at break (E_b) decrease gradually with aging period as compared to the unaged composites. Upon aging, swelling resistance increase initially indicating increased crosslink density of EPDM/Bt composite due to post‐curing and reduced after 4 days of aging due to crosslink destruction and EPDM chain scissioning. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4419–4427, 2013     

Influence of silica loading on the mechanical properties and resistance to oil and thermal aging of CR/NR blends

Blends of 75/25 chloroprene rubber(CR)/natural rubber (NR) filled with various loadings of precipitated silica were prepared and their processability and mechanical properties as well as their resistance to thermal aging and oil were determined. The blend morphology was also studied using the atomic force microscopy technique. The results reveal that the mixing energy and the Mooney viscosity of the compound are increased continuously with increasing silica loading. It is also found that both scorch and optimum curing times are shortened while the total crosslink density is increased with increasing silica loading. The positive effect on cure could be explained by the chemical reaction between the allylic chlorine atom of CR and the silanol group on silica surface. The tensile strength, modulus, and hardness of the blend vulcanizate are noticeably improved while the compression set at elevated temperature is impaired with increasing silica loading. The results also reveal that both thermal aging resistance and oil resistance of the blend vulcanizates, as represented by the relative properties, are enhanced with the addition of silica. The resistance enhancement is believed to arise from the combination of the dilution effect, the increased crosslink density and also the reduction of NR dispersed phase size. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Thermal property improvement of ethylene‐octene copolymer through the combined introduction of filler and silane crosslink

In many applications, e.g., wire and cable insulation, hot water pipe, high‐temperature properties of polymer are essential. This article presents the use of silane crosslinking together with the addition of particular filler in improving the thermal and mechanical properties of ethylene‐octene copolymer (EOC). The effects of filler surface characteristics on siloxane network structure developed and final properties of the crosslinked products are discussed. The results show an increase in the decomposition temperature of EOC more than 50°C after modification. Only crosslinked composites are able to withstand the high‐temperature environment of aging test which is beyond the melting temperature of the matrix polymer. The crosslinked composites filled with calcium carbonate show superior properties to those with silica, due to a higher crosslink density and tighter network structure formed. The silane coupling mechanism and the presence of bound polymer on silica surfaces cause difficulties for the crosslink formation in the silica filled systems. However, an advantageous influence of both silane coupling and crosslink reaction in the silica filled composites is seen on the enhanced tensile strength and modulus of the materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The interplay of physical aging and degradation during weathering for two crosslinked coatings

Polymer molecular relaxation, or ‘physical aging’, is a very important influence on permeability and mechanical properties of any polymer below its glass transition. ‘Physical aging’ occurs as even an unstressed polymer gradually relaxes towards its equilibrium conformation. This and the shorter term response to stress happen over periods much longer than the typical cycle of an accelerated weathering test, thus important properties of a polymeric coating may be affected by the difference in frequency between natural and artificial exposures, in addition to other factors. Further, ‘physical aging’ is affected by chemical changes to the polymer network caused by the degradation during a weathering exposure. In this investigation, purely physical aging was compared with the effect of concurrent chemical degradation by measuring ‘enthalpy recovery’ and mechanical stress relaxation at a variety of temperatures and at various stages during accelerated weathering exposure. The effect of physical aging was quite apparent in both an epoxy-polyamide coating and a polyester-urethane coating. Changes in physical aging behaviour during degradation were different for the two coatings, which points to further reasons for discrepancy between accelerated weathering and natural exposure.     

Effects of hot‐air aging and dynamic fatigue on the structure and dynamic viscoelastic properties of unfilled natural rubber vulcanizates

The effects of hot‐air aging and dynamic tensile fatigue on the network structure and dynamic viscoelastic properties of unfilled natural rubber (NR) vulcanizates were investigated with magnetic resonance crosslink density spectrometry, Fourier transform infrared spectroscopy/attenuated total reflection (FTIR–ATR), and dynamic mechanical analysis. The results showed that there was a carbonyl weak absorption peak at 1723 cm^?1 in the FTIR–ATR spectra of unfilled NR vulcanizates after hot‐air aging; The crosslink density decreased continuously as the aging time increased. The dynamic modulus of an aged specimen declined considerably, and the value of tan δ after 72 h of aging greatly increased. There was a large difference in the FTIR–ATR spectra of unfilled NR vulcanizates before and after tensile fatigue. The peaks at 1597, 1415, and 1015 cm^?1 increased concurrently with the tensile fatigue time. Initial analysis suggested that structures such as conjugated dienes appeared in the network structure. The modulus declined sharply, whereas the value of tan δ increased noticeably, after tensile fatigue. The effects of hot‐air aging and tensile fatigue on the crosslink density and FTIR–ATR spectra of unfilled NR vulcanizates were different, but both affected the viscoelastic properties dramatically. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

交联密度对氢化丁腈橡胶热性能的影响

用核磁共振法(NMR)测定了氢化丁腈橡胶(HNBR)的横向弛豫时间(T21),用以反映硫化胶的交联密度,并研究了交联密度对硫化胶热性能和力学性能的影响。结果表明:随着硫化剂DCP用量的增多,胶料交联密度增大,玻璃化转变温度升高,耐热性提高,拉伸强度先增大后减小,拉断伸长率、永久变形和撕裂强度明显减小。     

Temperature Dependence of Tensile Strength for a Woven Boron-Nitride-Coated Hi-Nicalon™ SiC Fiber-Reinforced Silicon-Carbide-Matrix Composite

The temperature dependence of tensile fracture behavior and tensile strength of a two-dimensional woven BN-coated Hi-Nicalon™ SiC fiber-reinforced SiC matrix composite fabricated by polymer infiltration pyrolysis (PIP) were studied. A tensile test of the composite was conducted in air at temperatures of 298 (room temperature), 1200, 1400, and 1600 K. The composite showed a nonlinear behavior for all the test temperatures; however, a large decrease in tensile strength was observed above 1200 K. Young's modulus was estimated from the initial linear regime of the tensile stress–strain curves at room and elevated temperatures, and a decrease in Young's modulus became significant above 1200 K. The multiple transverse cracking that occurred was independent of temperature, and the transverse crack density was measured from fractographic observations of the tested specimens at room and elevated temperatures. The temperature dependence of the effective interfacial shear stress was estimated from the measurements of the transverse crack density. The temperature dependence of in situ fiber strength properties was determined from fracture mirror size on the fracture surfaces of fibers. The decrease in the tensile strength of the composite up to 1400 K was attributed to the degradation in the strength properties of in situ fibers, and to the damage behavior exception of the fiber properties for 1600 K.     

Lead magnesium niobate-filled silicone dielectric elastomer with large actuated strain

A silicone dielectric elastomer filled with lead magnesium niobate with a maximum actuated strain of 7.4% at 45 kV/mm was fabricated by optimizing the amount of dielectric filler, amount of plasticizing agent, and crosslink density of the elastomer. The actuated strain of dielectric elastomers (DEs) is determined by both the dielectric constant and the elastic modulus. Although the dielectric constant of the silicone elastomer increased with increasing loading amount of lead magnesium niobate, actuated strain did not increase as expected because the elastic modulus increased at the same time. The elastic modulus of silicone dielectric elastomer was decreased by reducing the crosslink density or adding plasticizing agent, leading to a visible increase in actuated strain. It was also revealed that actuated strain of silicone dielectric elastomer always goes up with increasing ratio of dielectric constant to elastic modulus. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

An investigation of chemical crosslinking effect on properties of high-density polyethylene

High-density polyethylene (HDPE) was chemically crosslinked with various amounts of di-tert butyl cumyl peroxide (BCUP). Crosslink density determined by rubber elasticity theory using hot set test showed an increase with increasing BCUP. Glass transition temperature (T_g), thermal stability, crystallization, melting behavior and tensile properties were studied. The results showed a new finding about decrease in T_g as a consequence of the ‘chemical crosslinking’ of HDPE. This was explained by observed reduction in crystallinity and expected increase in free volume as a result of restriction in chain packing. However, chemical crosslinking had no significant effect on the thermal stability. The stress at break, Young's modulus yield strength and elongation at break generally decreased with increase in BCUP. By increasing the temperature for slightly crosslinked HDPE, the elongation at break was increased but by increasing the crosslinking level an opposite effect was observed. Crosslinked HDPE showed an decrease in creep strain and an increase in creep modulus with increasing BCUP.     

氢化羧基丁腈橡胶/环氧化POSS复合材料的硫化反应和性能研究

通过溶液共混和硫化成型制备了氢化羧基丁腈橡胶(HXNBR)/环氧环己基POSS复合材料,并进行了硫化性能、动态力学性能、FTIR谱图和交联密度测试。结果表明,环氧化环己基POSS和HXNBR发生交联反应并产生醇羟基;在实验温度范围内,200℃时复合材料硫化效率最佳,正硫化时间(t90)约为10min;复合材料高弹储能模量和交联密度随POSS用量的增大而明显增大,损耗因子降低,玻璃化转变温度提高;交联密度在20～40min区间增加幅度较大,当硫化时间为60min时交联密度有所降低。