一种低粘度双马树脂及其复合材料的性能研究

对一种适用于RTM工艺的低粘度双马树脂QY8911-Ⅳ进行了研究,考察了树脂体系的粘度特性和固化特性,并对不同后固化温度下的树脂固化物的耐热性、力学性能及吸水性等进行了全面考察。结果表明,该树脂体系具有粘度低(80℃为200mPa·s)、固化收缩小(1%)、耐热性好(T_g为260℃)、力学性能好(弯曲强度为170 MPa、冲击强度为20 kJ/m~2)和吸水率低(0.39%)等特点。选择合适的注射工艺和固化工艺,以此树脂为基体,采用RTM工艺,制备出了碳布增强的复合材料,并对其力学性能进行了测试,其弯曲强度和冲击强度分别为754 MPa和110.9 kJ/m~2。     

RTM成型用高性能环氧树脂基体的研究

将AG-80和TDE-86以一定比例混合,通过加入自配的低粘度液体固化剂,得到了一种适用于RTM工艺的树脂体系。结果表明,该树脂体系在30℃时的粘度为1081mPa.s,其树脂固化物的拉伸强度为73MPa,弹性模量达到1.36GPa,断裂伸长率为6.3%,弯曲强度为150MPa,弯曲模量为3.12GPa,玻璃化转变温度为191℃,该树脂体系不仅粘度低,还具有优异的力学性能和耐温性,可满足RTM成型工艺对环氧树脂体系的要求。     

Synthesis and characterization of chlorinated soy oil based epoxy resin/glass fiber composites

Composites with good toughness properties were prepared from chemically modified soy epoxy resin and glass fiber without additional petroleum based toughening agent. Chlorinated soy epoxy (CSE) resin was prepared from soybean oil. The CSE was characterised by spectral, and titration method. The prepared CSE was blended with commercial epoxy resin in different ratios and cured at 85°C for 3 h, and post cured at 225°C for 2 h using m‐phenylene diamine (MPDA) as curing agent. The cure temperatures of epoxy/CSE/MPDA with different compositions were found to be in the range of (151.2–187.5°C). The composite laminates were fabricated using epoxy /CSE/MPDA‐glass fiber at different compositions. The mechanical properties such as tensile strength (248–299 MPa), tensile modulus (2.4–3.4 GPa), flexural strength (346–379 MPa), flexural modulus (6.3–7.8 GPa) and impact strength (29.7–34.2) were determined. The impact strength increased with the increase in the CSE content. The interlaminor fracture toughness (G_IC) values also increased from 0.6953 KJ/m² for neat epoxy resin to 0.9514 KJ/m² for 15%CSE epoxy‐modified system. Thermogravimetric studies reveal that the thermal stability of the neat epoxy resin was decreased by incorporation of CSE. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

高性能、低成本复合材料用环氧体系的研究

通过凝胶化测试和示差扫描量热分析(DSC)研究了CYD128环氧树脂/部分钝化间苯二甲胺固化体系的反应特性,测试了该体系浇铸体的力学性能和耐热性。设计了一种新型低成本真空辅助传递模塑(VARTM)成型工艺并研究了该成型工艺对复合材料力学性能的影响。结果表明,浇铸体弯曲强度可达131.0 MPa,拉伸强度71.8 MPa,拉伸模量3.1 GPa,冲击强度37.5 kJ/m2,玻璃化温度(Tg)98.1℃。使用新工艺得到的复合材料力学性能优异,其中连续玻璃纤维、连续碳纤维增强复合材料弯曲强度分别达到950.2 MPa、1 097.4 MPa。     

一种回转体类构件用中低温固化环氧树脂体系研究

采用等温黏度实验和浇铸体力学性能测试来优选自制改性固化剂CUR–1的配比,通过不同升温速率下的固化过程差示扫描量热并对固化物进行傅立叶变换红外光谱分析,确定了体系的固化制度,研制出一种适用于发动机壳体或结构复杂的回转体类结构件的碳纤维湿法缠绕树脂基复合材料的中低温固化环氧树脂体系,用湿法缠绕工艺制作单向纤维缠绕成型复合材料环(NOL环)并进行了性能测试。结果表明:当CUR–1的含量为15份时,树脂体系具有适于湿法缠绕工艺的黏度和使用期,树脂可在80℃完全固化,同时浇铸体拉伸强度为84 MPa,拉伸弹性模量为3.8 GPa,断裂伸长率为5.4%,热变形温度为131℃。该树脂体系与纤维粘结性好,NOL环力学性能高,NOL环拉伸强度为2 451 MPa,拉伸弹性模量为146 GPa,层剪切强度为55 MPa。     

碳纤维湿法缠绕用环氧树脂基体研究

以TDE-85树脂和AFG-90树脂为主体树脂,混合芳香胺为固化剂,研究了一种适合于碳纤维复合材料湿法缠绕成型的树脂配方。结果表明,该树脂的黏度低(＜550 mPa·s)、适用期长,其浇铸体具有优异的力学性能,其拉伸强度为107 MPa,拉伸模量为4．09 GPa,弯曲强度为161 MPa,弯曲模量为3．88 GPa,断裂伸长率超过6%。用其制备的T-700碳纤维缠绕复合材料界面粘接好,NOL环层间剪切强度达到66．8 MPa,拉伸强度达到2．44 GPa。     

Fabrication of highly isotactic polypropylene fibers to substitute asbestos in reinforced cement composites and analysis of the fiber formation mechanism

Highly isotactic polypropylene (PP) is currently studied as a cement‐reinforcement fiber that could potentially be substituted for asbestos because of its resistance to prolonged high‐temperature curing. The higher the isotacticity of the PP fiber is, the higher the tensile modulus and breaking strength of the cured fiber are. The PP fiber that exhibits a isotacticity of 99.6% (XI) and draw ratio of 6.0 retains a tensile modulus of 4.23 GPa, even after high‐temperature curing at 175°C for 5 h. PP fiber is cut into 6‐mm lengths and dispersed throughout a cement mixture to prepare a reinforced cement composite. The mixture is cured in an autoclave at 175°C for 5 h. The Charpy impact strength and flexural strength of the obtained cement composite tends to increase with increasing PP isotacticity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 981‐988, 2013     

Bio-resourced eugenol derived phthalonitrile resin for high temperature composite

Eugenol (EG) is an abundant renewable compound that has been widely used in the synthesis of bio-based thermosetting resin, but there are few reports on the phthalonitrile (PN) resin derived from EG. In this study, a new kind of bio-based PN resin (MEG-PN) derived from EG derivative was successfully synthesized. PN is a traditional class of high-performance thermosets with poor processability for its ultra-high melting point and curing temperature. The MEG-PN resin possesses excellent processability: its melting temperature is much lower (77°C), and it can be cured at a moderate temperature (281°C) in the absence of curing agents. The cured MEG-PN resin exhibited great heat resistance according to its 5% weight loss temperature at 448°C and its char yield percentage as high as 75.6% at 800°C under nitrogen. The properties of the carbon-fiber reinforced MEG-PN composite were comparable to those of petroleum-based PN resins: the glass transition temperature was around 397°C; the flexural strength and modulus were as high as 756 MPa and 119 GPa, respectively. Overall, a bio-based PN thermoset with great comprehensive performance was synthesized possessing the potential in the application of advanced composite.     

Preparation and properties of a new polytriazole resin made from dialkyne and triazide compounds and its composite

A new kind of polytriazole resins were prepared from a triazide and a dialkyne compounds and characterized. These resins can be cured at 80 °C. The curing process for a resin was traced by FT-IR. The glass transition temperature T_g and thermal decomposition temperature T_d5 of the cured resin with the molar ratio of azide group to alkyne group [a]/[b]=1.0:1.0 reach 216 °C and 360 °C, respectively. The flexural strength of the cured resin and its glass fiber reinforced composite arrive at 183.6 MPa and 963.4 MPa, respectively. The resin would be a good candidate for the matrices of advanced composites.     

间苯二酚二缩水甘油醚的制备及其应用

采用三苯基磷作醚化催化剂,粉状氢氧化钠作闭环剂合成了间苯二酚二缩水甘油醚(RDGE),其环氧值为0.80,在25℃时粘度为0.36 Pa.s,示差扫描量热仪(DSC)检测表明,其固化放热峰比双酚A型环氧树脂(E51)降低了约15℃。RDGE对E51有非常显著的稀释作用,二者共混,大大提高了通用环氧树脂的综合性能。采用593#固化剂时,RDGE和E51的拉伸强度分别为75.17 MPa和58.58 MPa,前者比后者高出28%,RDGE与E51共混固化物的拉伸强度随RDGE含量的增加而呈线性增加;593#固化的RDGE/E51共混体系,弯曲强度和弯曲模量均随RDGE用量的增加而呈线性增加,弯曲强度由E51的112.77 MPa增加到RDGE的123.75 MPa,弯曲模量由E51的1.79 GPa增加到RDGE的2.40 GPa。     

Bismaleimide resin modified with diallyl bisphenol A and diallyl p‐phenyl diamine for resin transfer molding

O,O′‐diallyl bisphenol A (DBA) and N,N′‐diallyl p‐phenyl diamine (DPD) were used for the reactive diluents of 4,4′‐bismaleimidodiphenol methane (BDM). The objective was to obtain a modified BDM resin system suitable for resin transfer molding (RTM) process to prepare the advanced composites. The processing behavior was determined by time–temperature–viscosity curves, gel characteristics, and differential scanning calorimetry (DSC). The injection temperature of the resin system in RTM could be 80°C, at which its apparent viscosity was only 0.31 Pa/s, and the apparent viscosity was still less than 1.00 Pa/s after the resin was held at 80°C for 16 h. The gel time test result indicated that at low temperatures, the reactivity of the resin system is low, whereas at high temperatures, the resin could cure very fast, which was beneficial to RTM. The postcure of the cured resin at a given temperature was necessary because the resin had a wide and flat cure exothermic peak, observed by DSC curve. The cured resin displayed both high heat and hot/wet resistance and high mechanical properties, especially tensile strength, tensile modulus, and flexural strength at room temperature, which reached 96.2 MPa, 4.8 GPa, and 121.4 MPa, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2245–2250, 2001     

Mechanical,thermal, electrical,and interfacial properties of high‐performance bisphthalonitrile/polyarylene ether nitrile/glass fiber composite laminates

Bisphthalonitrile (BAPh)/polyarylene ether nitrile end‐capped with hydroxyl groups (PEN‐OH) composite laminates reinforced with glass fiber (GF) have been fabricated in this article. The curing behaviors of BAPh/PEN‐OH prepolymers have been characterized by differential scanning calorimetry and dynamic rheological analysis. The results indicate that with the introduction of PEN‐OH the curing temperature of BAPh has decreased to 229.6–234.8°C and BAPh/PEN‐OH prepolymers exhibit large processing windows with relatively low melt viscosity. The BAPh/PEN‐OH/GF composite laminates exhibit tensile strength (272.4–456.5 MPa) and modulus (4.9–10.0 GPa), flexural strength (507.1–560.9 MPa), and flexural modulus (24.0–30.4 GPa) with high thermal (stable up to 538.3°C) and thermal stabilities (stable up to 475.5°C). The dielectric properties of BAPh/PEN‐OH/GF composite laminates have also been investigated, which had little dependence on the frequency. Meanwhile, scanning electron microscopy results show that the BAPh/PEN‐OH/GF composite laminates display excellent interfacial adhesions between the matrix and GFs. Herein, the BAPh/PEN‐OH matrix can be a good matrix for high‐performance polymeric materials and the advanced BAPh/PEN‐OH/GF composite laminates can be used under high temperature environment. POLYM. COMPOS., 34:2160–2168, 2013. © 2013 Society of Plastics Engineers     

RTM工艺用双酚F型环氧树脂体系研究

本文选用二乙烯三胺和二乙氨基丙胺作固化剂,系统地研究了用于RTM工艺的低粘度双酚F型环氧常温固化体系的工艺特性及力学性能。研究结果表明,用二乙烯三胺固化双酚F型环氧时,其固化物力学性能优异,但适用期较短;用二乙氨基丙胺部分替代二乙烯三胺,得到了适用期为36m in的树脂体系(二乙烯三胺用量2phr、二乙氨基丙胺用量4phr),其树脂固化物拉伸强度为66.8MPa,弯曲强度为102.0MPa。用所确定的树脂体系制得的碳纤维复合材料综合力学性能优良,树脂与碳纤维界面粘结良好,将其应用于RTM成型某型号舱段的制备,制品综合性能优良。     

Synthesis,characterization, and cure of allyl and propargyl functionalized indene as a thermoset composite matrix resin

Two highly functionalized resins were synthesized by the phase transfer reaction of indene with propargyl bromide or allyl chloride in the presence of strong base. The resins consisted of a mixture of tri- and tetrafunctional indenes with 60–80% of the product being tetrafunctional. The allylated (AL) and propargylated (PL) indene resins were thermally cured without added catalysts. Both resins exhibited a broad, highly exothermic cure with a peak energy at 320°C for AL resin and 282°C for PL resin. Thermal degradation of cured AL resin was found to begin at approximately 400°C with a carbon yield of 20% of its initial weight at 1000°C. Carbon yields for cured PL resin were excellent, with 68% retention of weight at 1000°C. Unidirectional, carbon fiber composites were fabricated from the substituted indene resins. AL–carbon fiber composites gave modulus values of 126 GPa and strength values of 967 MPa, while PL–carbon fiber composites gave modulus values of 116 GPa and strength values of 935 MPa in three-point bending tests. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 475–482, 1998     

An epoxy resin-elastomer system for filament winding

Tests characterizing an epoxy system that contains 5 percent rubber and is suitable for wet-filament winding are described. The resin is a bisphenol-A rubberized epoxy diluted with an aliphatic diglycidyl ether and cured with an aromatic amine. The viscosity and pot life were measured and the progress of cure was monitored so an optimum cure could be chosen. Mechanical tests were performed on the cured resin. The low viscosity (0.95 Pa's) and long pot life (29.3 h) make for ease of processing. A cure cycle of 1.5h at 90°C plus 2 h at 130°C gives a cured resin having a glass transition temperature of 104°C. The heat-cured material has a tensile strength of 76.1 MPa and a modulus of 2.43 GPa. Kevlar 49 composites of 60-, 65-, and 70-volume-percent fiber were prepared and tested. Results are presented and compared to two other Kevlar 49/epoxy composites.     

Development and application of triglyceride-based polymers and composites

Triglyceride oils derived from plants have been used to synthesize several different monomers for use in structural applications. These monomers have been found to form polymers with a wide range of physical properties. They exhibit tensile moduli in the 1–2 GPa range and glass transition temperatures in the range 70–120 °C, depending on the particular monomer and the resin composition. Composite materials were manufactured utilizing these resins and produced a variety of durable and strong materials. At low glass fiber content (35 wt %), composites produced from acrylated epoxidized soybean oil by resin transfer molding displayed a tensile modulus of 5.2 GPa, a flexural modulus of 9 GPa, a tensile strength of 129 MPa, and flexural strength of 206 MPa. At higher fiber contents (50 wt %) composites produced from acrylated epoxidized soybean oil displayed tensile and compression moduli of 24.8 GPa each, and tensile and compressive strengths of 463.2 and 302.6 MPa, respectively. In addition to glass fibers, natural fibers such as flax and hemp were used. Hemp composites of 20% fiber content displayed a tensile strength of 35 MPa and a tensile modulus of 4.4 GPa. The flexural modulus was ∼2.6 GPa and the flexural strength was in the range 35.7–51.3 MPa, depending on the test conditions. The flax composite materials had tensile and flexural strengths in the ranges 20–30 and 45–65 MPa, respectively. The properties exhibited by both the natural- and synthetic fiber-reinforced composites can be combined through the production of “hybrid” composites. These materials combine the low cost of natural fibers with the high performance of synthetic fibers. Their properties lie between those displayed by the all-glass and all-natural composites. Characterization of the polymer properties also presents opportunities for improvement through genetic engineering technology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 703–723, 2001     

Synthesis and characterization of a new class of thermosetting resins: Allyl and propargyl substituted cyclopentadiene derivatives

A series of all-hydrocarbon resins were synthesized by reacting cyclopentadiene allyl chloride, propargyl chloride, or a mixture of allyl chloride and propargyl ide, under phase transfer conditions. Phase transfer reactions with and without added solvents, and with either quaternary ammonium or crown ether catalysts, yielded similar products consisting of a mixture of 1,1-disubstituted cyclopentadiene (minor amount) and 2-3 isomers each of tri-, tetra-, penta-, and hexa-substituted derivatives. No further reaction of each these components possible. The overall substitution pattern varied little with changes in reaction conditions although limiting the allyl chloride content led to still reactive, partially substituted products. Incorporation of all-propargyl and high propargyl-to-allyl mixed functionalities on cyclopentadiene yielded products whose stability was very hindering their thorough characterization. Preliminary evaluation was there-carried out for mixed resins with lower propargyl functionality. The allyl substituted resin (allylated cyclopentadiene, ACP) underwent thermal cure lout initiator at around 200°C while allyl/propargyl substituted resin (7:1 ratio, APCP) showed a faster, lower temperature cure at around 120°C. Cationic cure of ACP was also initiated by a novel sulfonium salt at around 100°C. Neat resin when cured at 200°C gave material with a flexural storage modulus 2 of about 300 MPa. Further cure at 250°C raised the modulus to 1.2 GPa. resin gave composites with excellent properties when used with glass and on fibers. Flexural modulus values (by DMA) of ∼ 66 GPa were obtained for ACP/carbon fiber composites compared with 42 GPa for epoxy/carbon composites made in our laboratories using commercially available materials. The modulus values at 300°C dropped to 10% of the room temperature value for the epoxy composites, while the ACP/carbon composite maintained 60% of its room temperature value at 300°C. When brought back to ambient temperature, the modulus of latter sample had increased to 80 GPa and that of the epoxy composite dropped to 23 GPa. Glass fiber ACP composites performed similar to an epoxy composite up to 200°C but maintained properties up to 300°C while those of the epoxy were drastically reduced. TGA analysis of both cured ACP resin and its composites showed decomposition beginning at 375°C. Three-point-bending tests indicated very high modulus with brittle failure for ACP composites. Scanning electron micrographs showed moderate bonding of the new resin to both carbon glass fiber surfaces. This new class of thermosetting resins offers excellent potential for application in low-cost glass and carbon composites with good thermal and physical properties.     

A new bismaleimide system for resin transfer molding

A new bismaleimide (BMI) resin system, designated 4503A, suitable for resin transfer molding (RTM) has been developed. It is prepared by employing allyl methyl phenol and diallyl bisphenol A as reactive diluents for BMI. The processing properties of 4503A were investigated by time-temperature-viscosity curves, gel characteristics, and differential scanning calorimetry (DSC). Data show that the injection temperature of 4503A prepolymer can be as low as 75°C, while its viscosity is only 0.34Pa · s. In addition, after being maintained at 75°C for 12h, the viscosity is <0.95Pa · s. The cured 4503A resin has a glass transition temperature (T_g) and a heat deflection temperature (HDT) of 266 and 232°C, respectively; properties include tensile strength of 81MPa, flexural strength of 108MPa, and G_1C of 213J/m². Other properties of a composite based on 4503A system and woven glass cloth are also discussed. Regarding short beam shear (SBS) strength, for tests at 150 and 180°C, 80 and 61% of the original room temperature (RT) strength is retained. A similar strength retention (86 and 68%) is noted for flexural properties.     

Preparation and properties of biocomposites composed of epoxidized soybean oil,tannic acid,and microfibrillated cellulose

As a new biobased epoxy resin system, epoxidized soybean oil (ESO) was cured with tannic acid (TA) under various conditions. When the curing conditions were optimized for the improvement of the thermal and mechanical properties, the most balanced properties were obtained when the system was cured at 210°C for 2 h at an epoxy/hydroxyl ratio of 1.0/1.4. The tensile strength and modulus and tan δ peak temperature measured by dynamic mechanical analysis for the ESO–TA cured under the optimized condition were 15.1 MPa, 458 MPa, and 58°C, respectively. Next, we prepared biocomposites of ESO, TA, and microfibrillated cellulose (MFC) with MFC contents from 5 to 11 wt % by mixing an ethanol solution of ESO and TA with MFC and subsequently drying and curing the composites under the optimized conditions. The ESO–TA–MFC composites showed the highest tan δ peak temperature (61°C) and tensile strength (26.3 MPa) at an MFC content of 9 wt %. The tensile modulus of the composites increased with increasing MFC content and reached 1.33 GPa at an MFC content of 11 wt %. Scanning electron microscopy observation revealed that MFC was homogeneously distributed in the matrix for the composite with an MFC content of 9 wt %, whereas some aggregated MFC was observed in the composite with 11 wt % MFC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

高性能环氧树脂浇铸体研究

采用多官能缩水甘油胺型环氧树脂为基体,甲基四氢苯酐(MeTHPA)为固化剂,BH-1为促进剂,制备了环氧树脂浇铸体。研究了该体系的凝胶时间,粘度随温度的变化和固化特性,确定了最佳固化工艺,并对浇铸体进行了弯曲和拉伸等力学性能测试。结果表明:体系最佳固化条件为80℃/2 h+100℃/1 h+120℃/1 h,然后在150℃下后处理2 h。浇注体弯曲强度和拉伸强度分别达到202 MPa和99.9 MPa,弯曲模量和拉伸模量分别达到4.26 GPa和3.48 GPa,玻璃化转变温度为160.85℃,具有较低的粘度、良好的浸渍性,耐热性和优异的力学性能。