不饱和聚酯树脂的原位同时增韧和降收缩研究

不饱和聚酯树脂(UPR)的应用非常广泛，但是由于其固化收缩率高和固化物韧性差，使其应用受到了影响。文中在总结大量增韧和降收缩研究的基础上，合成了一系列添加剂，可以同时起到增韧和降收缩的作用。除此之外，还考察了同时增韧和降收缩的UPR体系的其它力学性能和热性能以及微观形貌。将合成的添加剂与商品降收缩剂H-870的效果进行了综合比较，结果表明，QS-MB不仅有很好的增韧作用，而且可作为低收缩剂使用，而后者则不具增韧效果。     

低轮廓不饱和聚酯树脂的中低温固化形态

研究了加有低轮廓添加剂的不饱和聚酯树脂在中低温固化时的形态,结果表明:温度对加入聚醋酸乙烯酯类LPA试样的固化形态影响不大,而加入聚苯乙烯类LPA对试样的固化形态则有较大的影响.在固化过程中极性较大的LPA更有利于从UPR相中分离出来,形成有利于补偿收缩的两相交互连续的相态结构,而玻璃转化温度与UPR的差别大并且低于固化温度的LPA,使得固化试样形成微孔有更多的时间和更高的效率对于加入聚醋酸乙烯酯类LPA的试样,试样的固化形态随着LPA含量的增加发生两次明显的转变.对于具有较高分子量的LPA,只需要加入较低的含量就能使试样形成相互连续的两相结构,而加入聚苯乙烯类LPA的试样,固化的形态随着LPA含量的增加没有明显的改变.     

热塑性树脂增韧酚醛树脂基复合材料研究

研究热塑性树脂的含量、端基、分子量对酚醛树脂基复合材料性能的影响，用扫描电镜观察增韧体系的断口形貌，对增韧机理进行了探索。结果表明，以热塑性树脂膜和固化后的酚醛树脂膜形成连续相、酚醛树脂固化球粒为分散相的“网膜-球粒”结构使酚醛树脂基复合材料的韧性提高。     

液体聚硫聚脲增韧环氧树脂形态结构的研究

以液体聚硫聚脲齐聚物来增韧环氧-聚酰胺体系,用DMTA和SEM研究了固化后环氧树脂的形态结构、相分离程度和增韧效果．结果表明,液体聚硫聚脲齐聚物的用量、齐聚物中聚脲含量对固化后的环氧树脂玻璃化温度、模量及形态有较大影响。随增韧剂中聚脲含量的提高,固化物的玻璃化温度、相分离程度及模量增加,同时固化物韧性增加。     

聚醚砜-环氧树脂共混体系相分离过程的数值模拟

在热塑性聚醚砜（PES）增韧改性热固性环氧树脂复合材料的制备过程中,通过控制PES-环氧树脂树脂共混体系相分离过程实现共混物相结构的调控,能够明显改善热固性环氧基体树脂的冲击强度。考虑PES-环氧树脂共混体系在相分离过程中PES应力松弛现象以及环氧树脂固化反应现象,采用黏弹性模型描述微观相形态的具体演化路径,揭示了树脂共混体系相分离过程的机制及动力学过程,分析了PES含量、PES分子量大小、PES与环氧树脂的动力学不对称程度以及固化工艺条件等材料及工艺参数对共混体系相结构演变过程以及最终相形态的影响规律及程度,从而为优化PES-环氧树脂树脂共混体系的微观相结构打下基础。     

环氧树脂网链结构对CTBN增韧作用的影响

本文通过改变反应型固化剂(70~#酸酐)用量及环氧树脂分子量,制得了两类网链结构相的似、但交联密度不同的纯环氧固化体系及加有橡胶的增韧体系。根据其微观形态、机械性能、以及交联点间平均网链长度,表明环氧树脂网链结构对增韧效果有很大的影响。实验还表明在CTBN—环氧树脂增韧体系的拉伸破坏过程中,存在着孔洞化和剪切屈服两种主要的形变方式,基质的屈服形变是破坏过程中吸收能量的主要途径。     

聚丙烯/-1,2-聚丁二烯共混物的形态结构及性能

本文研究了乙烯基含量不同与分子量不同的1,,2-聚丁二烯(1,2-PB)与基聚丙烯(PP)共混物的形态结构和性能。结果表明,1,2-PB 与 PP 具有一定的相容性,相容程度与乙烯含基量有关。1,2-PB 的加入,使 PP 相邻球晶产生片层相互交叉的界面结构,又使 PP 有β型结晶生产。1.2-PB 的最隹增韧效果可与乙丙橡胶相比拟。     

无机纳米粒子增韧改性不饱和聚酯树脂的研究进展

综述了近年来各种无机纳米粒子对不饱和聚酯树脂( UPR)增韧改性的研究现状.重点介绍了无机纳米粒子用量、粒子尺寸、表面改性处理等因素对改性UPR性能的影响.阐述了纳米粒子增韧增强UPR的机理.指出无机纳米粒子改性UPR中存在的问题和可能的发展方向.     

采用低黏度添加剂的环氧树脂增韧体系

本研究对3种低黏度添加剂作为2种环氧树脂体系增韧剂的性能进行了评价，2种环氧树脂体系1种为低活性的双酚A二缩水甘油醚(DGEBA)与胺类固化剂二乙基甲苯二胺体系，另1种为四缩水甘油基亚甲基二苯胺(TGDDM)环氧树脂与脂环族二胺类固化剂体系，所评价的增韧剂分别是端环氧基脂肪族聚酯型超支化聚合物、端羧基聚丁橡胶和端氧丙基硅氧烷。研究结果表明：端环氧基超支化聚酯可有效增韧低交联度的环氧树脂体系，即DGEBA基树脂体系，其最大的特点是添加剂对树脂体系的加工参数如黏度和凝胶时间无影响，当添加剂质量分数为15％时材料的断裂性能提高54％，同时对固化物的Tg无影响，该结果应归因于相分离产生的多相微粒形态能诱发粒子气穴化，同时使残余环氧树脂基本不溶解到固化后的连续环氧树脂基体中；橡胶类添加剂也可达到相同水平的增韧效果，但却会导致Tg下降10～20℃、初始黏度上升30％；硅氧烷类添加剂不能提高DGEBA基树脂体系的韧性，因为硅氧烷在环氧基体中分散性很差；对于TGDDM基树脂体系，3种添加剂均不能起到增韧作用。因为该环氧体系交联度过高而缺乏塑性形变。     

超支化环氧树脂改性苯并口恶嗪树脂的制备与性能

采用兼有脂肪族和芳香族结构的超支化环氧树脂(HBER)增韧改性苯并口恶嗪树脂(MDA),制备出不同质量比的MDA/HBER均相共混体系。通过傅里叶变换红外光谱、差示扫描量热及动态力学性能分析仪研究了共混体系固化行为和交联网络结构。利用流变仪对共混体系进行动态黏度测试,结果表明在60~190℃之间出现一段较宽的低黏度平台。力学性能测试表明,当HBER质量分数为10%时,共混固化物弯曲性能最优,韧性最佳。共混固化物断面形貌呈现出原位增韧增强特征。     

黏结剂相对分子质量对浇注PBX固化应力的影响?

采用自行研制的固化应力测试装置,测量了端羟基聚丁二烯(HTPB)基浇注高聚物黏结炸药(PBX)固化过程的应力变化,计算出固化应力数据,分析了黏结剂相对分子质量对热固性浇注PBX固化应力的影响,并对其在不同固化温度下的黏结强度进行了测试。结果表明:同一固化温度时,随着HTPB相对分子质量的逐渐增大,浇注PBX在固化阶段的最大热应力及收缩应力都逐渐减小。固化温度为100℃时,相对分子质量为1 500、2 800、4 000的HTPB基固化物因固化反应所产生的最大热应力分别为2.14、1.12、1.01 MPa,最大收缩应力分别为0.29、0.22、0.15 MPa。在固化降温阶段,HTPB相对分子质量越大,浇注PBX的收缩应力也越大。HTPB相对分子质量相同时,固化物的黏结强度随着固化温度的升高而降低;而固化温度一定时,HTPB相对分子质量对浇注PBX的黏结强度影响不大。     

热养护过程中超高性能混凝土的收缩性能研究

热养护能够提高UHPC的强度和减小UHPC的干燥收缩,已经广泛应用于工程实践中。主要研究了UHPC在热养护过程中的收缩变形性能和不同热养护龄期下UHPC的微观结构。结果表明,在热养护过程中,UHPC在50℃以内基本不发生收缩,当温度接近70℃时,收缩值迅速增加,最终的收缩值为450×10-6;随着配筋率的提高,UHPC在热养护过程中的收缩减小。热养护后,基体变得致密,Ca(OH)2的含量大幅减少,水化程度大大提高。     

Expansive concrete cured in pressurized water at high temperature

Behaviours of expansive concretes cured in pressurized water at high temperature (TPC curing) are investigated with regard to their variations in strain, weight and strength. These behaviours are compared with those cured by autoclave curing (AC curing) at the same pressure and temperature. The experimental data show that both of these curing methods are effective in reducing autogenous shrinkage and drying shrinkage at longer age after the curing. Particularly when TPC curing is adopted, the required expansion of concrete can be attained at smaller dosage of expansive agents, and after the curing length changes due to hygrometric or hygroscopic conditions are almost eliminated for later age. Therefore, this curing method is anticipated to be effective in introducing chemical prestress in a reinforced concrete member, which is proved by loading tests of spirally reinforced pipe specimens [Ei.-i. Tazawa, K. Miyaguchi, in: Proceedings of the 25th JUCC Congress on Cement and Concrete, 1998, pp. 71–76].     

Study on the polyethersulfone/bismaleimide blends: morphology and rheology during isothermal curing

The morphology and rheological behave of the polyethersulfone/bismaleimide blends during isothermal curing was investigated by rheological instrument, different scanning calorimetry (DSC), scanning electronic microscopy (SEM) and time resolved light scattering (TRLS). The influences of the PES content, the PES molecular weight and the curing temperatures on the complex viscosity of the blends were discussed in detail, which suggested that the fluctuation of the complex viscosity at the beginning of phase separation was largely dependent on the PES content, while the PES molecular weight mainly influenced the onset of phase separation and had relatively less influence on the evolution of complex viscosity. Moreover, the evolution of complex viscosity of blends with high PES content was relatively less sensitive to the curing temperature. In addition, it was found that the phase morphology as well as the composition of continuous phase played an important role in the rheological behavior of PES modified bismaleimide resin during isothermal curing.     

Compressive strength and drying shrinkage of fly ash-bottom ash-silica fume multi-blended cement mortars

This paper studies the physical properties, compressive strength and drying shrinkage of multi-blended cement under different curing methods. Fly ash, ground bottom ash and undensified silica fume were used to replace part of cement up to 50% by weight. Specimens were cured in air at ambient temperature, water at 25, 40 and 60 °C, sealed with plastic sheeting for 28 days. The results show that absorption and volume of permeable pore space (voids) of blended cement mortars at 28 day under all curing methods tend to increase with increasing silica fume replacement. The compressive strength of blended cement with fly ash and bottom ash was lower than that of Portland cement control at all curing condition while blended cement with silica fume shows higher compressive strength. In addition, the compressive strength of specimens cured with water increased with increasing curing temperature. The drying shrinkage of all blended cement mortar cured in air was lower than that of Portland cement control while the drying shrinkage of blended cement mortar containing silica fume, cured with plastic sealed and water at 25 °C was higher than Portland cement control due to pore refinement and high autogenous shrinkage. However, the drying shrinkage of blended cement mortar containing SF cured with water at 60 °C was lower than that of Portland cement control due to lower autogenous shrinkage and the reduced microporosity of C–S–H.     

Cure shrinkage characterization and modeling of a polyester resin containing low profile additives

Resin Transfer Moulding (RTM) has great potential as an efficient and economical process for fabricating large and complicated composite structural components. The low capital investment cost required and process versatility in component integration and assembly make RTM very attractive for high volume automotive applications. One of the challenges facing the automotive field is the resulting surface finish of manufactured components. The shrinkage associated with the curing of thermoset resins contributes to the poor surface quality. Low profile additives (LPA) are added to the resin to compensate for the cure shrinkage; however their effects on the thermal, rheological and morphological properties of polyester resins are not well understood. In this paper, the effect of LPA on cure kinetics, cure shrinkage and viscosity of a polyester resin is studied through differential scanning calorimetry (DSC) and special rheological techniques. Models are developed to predict cure shrinkage, LPA expansion, cure kinetics and viscosity variations of the resin as a function of processing temperature. Finally, morphological changes in the resin with and without LPA, during isothermal cure, are studied with hot stage optical microscopy. The results show that the LPA content in the range tested had no significant effect on the cure kinetics. However, higher LPA content reduced cure rate and cure shrinkage. A minimum of 10% LPA was required to compensate for cure shrinkage. Shrinkage behavior of all formulations was similar until a degree-of-cure of 0.5. However, resin formulations with higher LPA content showed expansion at later stages during curing.     

Effects of MgO-based expansive additive on compensating the shrinkage of cement paste under non-wet curing conditions

Expansive additives are widely used to compensate the drying shrinkage of cement-based materials to avoid cracking. However, the expansion of conventional ettringite-bearing expansive additive depends strongly on wet curing and is mainly generated at early age, and hence it may not work well in concretes without sufficient water supply or exhibit long-term shrinkage. MgO-based expansive additive, for which less water is needed for the formation of Mg(OH)₂ in comparison to ettringite, was prepared and its compensating effect on the autogenous shrinkage and late age thermal shrinkage of Portland and fly ash cement pastes at low water-to-cement ratio was investigated. The tests were conducted under sealed condition, so that the moisture exchange with the environment was prevented. Results show that, even under the non-wet curing condition, the shrinkages of cement pastes can be compensated effectively. Microstructure analysis by scanning electron microscope indicates that the macro-expansion of cement pastes is probably caused by the locally restrained expansion of MEA due to the hydration of MgO.     

聚芳基乙炔树脂基复合材料固化缺陷的产生机制

针对石英纤维增强聚芳基乙炔(PAA)树脂基复合材料固化微裂纹缺陷问题, 采用差示扫描量热、 红外光谱、 顶杆示差、 三点弯曲及金相分析等方法, 通过PAA树脂的固化反应、 收缩特性分析, 研究了树脂浇注体力学性能、 增强体结构形式、 纤维体积分数对裂纹缺陷产生的影响。结果表明, PAA树脂固化收缩率大、 树脂脆性是PAA复合材料中裂纹缺陷产生的主要原因, 提高纤维含量、 减少富树脂区有助于抑制裂纹缺陷, 并且采用酚醛树脂对PAA进行改性后, 亦可有效减少裂纹的产生。