Synthesis and performance of flexible epoxy resin with long alkyl side chains via click reaction

Epoxy resin is a thermosetting polymer with excellent performance and wide application. However, it suffers from low toughness and high brittleness because of its high crosslink density. To overcome these disadvantages, this study synthesizes a toughened, flexible, and hydrophobic epoxy resin (DGEBDBP) by introducing a flexible segment into the polymer network via a thiol-ene click reaction. The cured flexible epoxy resin is obtained by mixing E44, DGEBDBP, and polyamide curing agents of varying contents. The long alkyl side chains significantly improve the mechanical properties and hydrophobicity of the cured epoxy resin. The sample containing 75% DGEBDBP and 25% E44 achieve the highest breaking elongation that was nine times that of pure E44, the highest compressive strength of 112.8 MPa, and the highest contact angle of 101.4°. The introduction of side chains through the thiol-ene click reaction can provide a simple and effective method for designing and preparing multifunctional epoxy resins.     

Transparent and toughening epoxy thermosets modified by linear telechelic polymer containing rigid spiroacetal moieties: Uncovering the relationship between the heterogeneous crosslinked network and thermoset performances

Spiroacetal moieties containing linear telechelic polymers (LTPs) with two terminal epoxy groups were facilely synthesized via the successive thiol-ene and thiol-epoxy click additions. The LTPs were incorporated into epoxy matrix to fabricate the transparent and toughening thermosets. In term of the miscibility of epoxy with the adduct of ethanedithiol and 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane (BTU), it is proposed that the size of the formed nanostructures was small enough to allow light penetrate. Therefore, the modified thermosets were transparent, which was further confirmed by small-angle X-ray scattering (SAXS) measurements. The LTPs with an alternating structure of rigid spiroacetal moiety and soft thioether could formed heterogeneous crosslinked networks (HCNs) and obviously toughen epoxy thermosets. Flexural strength increased from 1.06 GPa for neat epoxy to 2.09 GPa for toughening thermosets modified with 15 wt% LTPs. The stress field intensity (K_IC) value reached up to 3.93 by more than 125% compared with that of the control sample (1.75). This work uncovered the role of HCNs on performance and paved a way for technological advances toward transparent and toughening materials in epoxy thermosets.     

顺北超深窄间隙固井技术应用

顺北区块超深窄间隙固井面临高温、井筒内压高交变以及高压盐水层等复杂工况,水泥环长效密封性难以保证。基于顺北12.7mm窄间隙固井工况,采用自主研制的窄间隙水泥环密封完整性评价装置,研究了水泥石密封失效机理,结果表明：加压养护的低弹性模量水泥石较常规水泥石具有更好的密封性能。在此基础上,通过优选弹性材料及配套外加剂,研制了增韧水泥浆体系,弹性模量可低至6.8GPa、抗压强度可达22.7MPa。进一步通过优化固井综合措施,形成了提高超深窄间隙井筒完整性的固井配套技术。基于该技术,现场应用1井次,固井质量优质,未发生水窜。研究成果对于超深井窄间隙固井具有重要借鉴意义,可有效推进顺北区块的长效、安全、高效开发。     

The synergistic effects of β-nucleating agent and ethylene–octene copolymer on toughening isotactic polypropylene

The mechanical properties of isotactic polypropylene (iPP) and ethylene–octene copolymer (POE) blends with or without β-nucleating agent (β-NA) were systematically studied. Results demonstrated that, after β-NA and POE were separately added, the impact strength of injection molded iPP samples increased. β-NA and POE were also found to have a synergistic toughening effect on iPP matrix, and the effect was significant. When the contents were 0.05 wt% β-NA and 10 wt% POE, the impact strength reached the maximum, i.e., almost 15 times that of neat iPP. SEM further revealed that POE in skin and core layers existed as long and narrow strips along the flow direction and throughout crystals. The tensile strength did not deteriorate because of the special phase morphology and tight interfacial interaction between POE phase and matrix. WAXD and DSC revealed that POE addition had negligible influence on crystal form, and a considerable number of β crystals was generated by adding β-NA. SEM results also confirmed a critical β-NA content. When β-NA content was lower than the critical value, perfect β sphaerocrystals were generated. When β-NA was higher, “bundle-like” crystal structures formed. Perfect β sphaerocrystals were more efficient for dissipating energy because of the looser stacking pattern, thus showing better toughness.     

GCr15单缝关节轴承外套圈强韧化热处理

本文研究ＧＣｒ１５钢单缝球关节轴承外套圈强韧化热处理工艺，分析强韧化组织与机械性能的直接关系，以及其强韧化机理．试验结果表明，低温淬火工艺可使外套圈获得优良强韧性与耐磨性．     

Properties of Poly(butylene terephthalate)/Bisphenol A Polycarbonate Blends Toughening with Epoxy-Functionalized Acrylonitrile–Butadiene–Styrene Particles

Glycidyl methacylate functionalized acrylonitrile–butadiene–styrene particles (ABS-g-GMA) prepared via an emulsion polymerization method were used to toughen poly(butylene terephthalate) (PBT)/bisphenol A polycarbonate (PC) blends. DMA results showed PBT was partially miscible with PC and the addition of ABS-g-GMA improved the miscibility between PBT and PC. DSC tests further testified that the introduction of ABS-g-GMA improved the miscibility of PBT and PC according to the T_m depression criterion. SEM displayed a very good dispersion of ABS-g-GMA particles in the PBT/PC blends and the dispersed phase size of PC decreased due to the compatibilization effect of ABS-g-GMA. The mechanical properties showed that the addition of 10 wt% ABS-g-GMA was sufficient to induce a super-tough fracture behavior to the PBT/PC blends and a notched impact strength of more than 1000J/m was achieved. The Vu-Khanh test showed that stable crack propagation took place for PBT/PC blends with the addition of ABS-g-GMA and led to ductile failure.     

Synergistic effect of SEBS-g-MA and epoxy on toughening of polyamide 6/glass fiber composites

Maleated styrene-ethylene-butylene-styrene block copolymer (SEBS-g-MA) and epoxy monomer, individually or in combination, are used to toughen polyamide 6/glass fiber composites. The epoxy monomer enhanced interaction between polyamide 6 and glass fiber. SEBS-g-MA rubber is uniformly dispersed in polyamide 6 matrix caused by the preferred compatibilizing reaction between the anhydride group of rubber and the amine terminal group of polyamide 6. The addition of epoxy does not affect the fine dispersion of SEBS-g-MA. Polyamide 6/glass fiber binary composites are brittle. The addition of epoxy monomer alone does not change their brittle features. Similarly, in the absence of epoxy monomer, adding 20 wt % of SEBS-g-MA to polyamide 6/glass fiber composites does not greatly increase the tensile ductility. Only when both SEBS-g-MA and epoxy monomer are present in some combination, do the polyamide 6/glass fiber composites show prominent ductile characteristics, such as stress-whitening and necking. This synergistic effect of epoxy monomer and SEBS-g-MA also imparts higher notched impact strengths to the ternary composites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1448–1458, 2007     

层间短纤维的Ⅱ型纤维桥联分析

对于层间加入增韧短纤维的连续纤维增强树脂层板的Ⅱ型层间增韧问题,考虑层间短纤维杂乱分布和几乎与层间裂纹平行的特点,基于基体剥落与纤维拉出耦合,考虑非桥联短纤维对剥离的干扰作用,建立了层间短纤维在Ⅱ型层间裂纹情况下的桥联模型.通过对不同角度桥联纤维拔出过程的分析,得到了桥联力与位移的关系.数值分析表明,除了角度接近90°的纤维外,拉出之前位移均很小,桥联力迅速增加,拉出过程中桥联力下降,位移大幅度增加,能量耗散主要发生在拉出阶段.随角度的增加,桥联力和能量耗散迅速减小.     

Cavitation of rubber particles in high-impact polystyrene: Effects of crosslinking by γ-irradiation

Tensile tests on high-impact polystyrene (HIPS) show that a 60 Mrad dose of γ-radiation raises the yield stress from 11.5 to 19.8 MPa, and the flow stress from 10.0 to 19.6 MPa, while reducing the elongation at break from 50 to 4%. Similar reductions in fracture resistance are observed in irradiated Charpy impact specimens. The T_g of the rubber phase shifts from −70 to −57 °C, and its estimated shear modulus increases from 0.1 to 0.5 MPa. It is concluded that the observed changes in mechanical properties are due almost entirely to crosslinking of the polybutadiene. This not only inhibits cavitation and fibrillation in the rubbery membranes of the “salami” particles, thereby delaying yield, but also makes the fibrillated membranes more resistant to further dilatation, so that rates of craze thickening in the polystyrene matrix are reduced. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2168–2180, 2004     

CeO_2－ZrO_2与Y_2O_3－ZrO_2两相复合材料增强、增韧性能

以化学共沉淀法所得超细粉为原料，设计两相复合材料的微观结构，讨论了材料的增强、增韧机理。结果表明，该材料具有很好的增强、增韧性能。经１５５０℃，４ｈ烧成的材料，测得其抗弯强度为９０１ＭＰａ，断裂韧性为１４．３０ＭＰａ·ｍ~（１／２）。关键词：