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S-186树脂在碳纤维缠绕成型复材中应用
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更新日期： 2021-7-14 |
碳纤维缠绕是一种复合材料连续成型方法，是将浸过树脂胶液的连续纤维或布带，按照一定规律缠绕到芯模上，然后固化脱模成复合材料制品。
Carbon fiber winding is a continuous molding method of composite materials, which is to wind continuous fibers or fabrics impregnated with resin glue on a core mold according to a certain rule, and then solidify and demold into composite products.
常用的湿法缠绕成型用基体树脂主要有不饱和聚酯和环氧树脂。要求树脂在室温或工作温度下具有一定的粘度及较长适用期。树脂浇注体及碳纤维复合材料须具有良好的力学性能和耐热性能。
Commonly used matrix resins for wet winding mainly include unsaturated polyester and epoxy resin. These resins are required to possess a certain viscosity and a long pot life at room temperature or work temperature. Resin cast body and carbon fiber composite must have good mechanical property and heat resistance.
S-186属于三官能度环氧树脂，其分子结构中含有一个脂环环氧基和两个缩水甘油酯基。
S-186 is a trifunctional epoxy resin with one alicyclic epoxy group and two glycidyl ester groups in its molecular structure.
特性 Characteristics
● 耐高温 150-200℃
Resistant to high temperature of 150-200℃
● 耐候性好
Good weatherability
● 高强度
High strength
● 高粘结性
High adhesion
S-186树脂克服了双酚A型环氧树脂耐候性差，抗冲击性能差等缺点，可用于制备高性能复合材料。
The resin S-186 has overcome the disadvantages of bisphenol A epoxy resins, including poor weatherability, poor anti-shock performance and so on. It can be used in production of high-performance composite materials.
由于S-186环氧树脂分子上的缩水甘油酯基具有较高的反应活性，所以该树脂比普通脂环族环氧树脂活性高。从而克服了一般脂环族环氧树脂对脂肪胺反应活性低，对咪唑及三级胺几乎不能固化的缺点。故S-186树脂既能酸酐固化又能胺类固化。
Due to its quite active glycidyl ester group, the resin S-186 has higher reactivity than ordinary cycloaliphatic epoxy resin, which can overcome the shortcomings of most cycloaliphatic epoxy resins such as low reactivity to aliphatic amines, almost non-curing effect on imidazole and tertiary amines. Therefore, the resin S-186 can be cured both by anhydrides and amines.
S-186树脂-酸酐固化体系
S-186 resin and anhydride curing system
● 常用的酸酐：邻苯二甲酸酐，四/六氢苯酐，甲基四/六氢苯酐，甲基纳迪克酸酐
Commonly used anhydrides: phthalic anhydride, tetra/hexahydrophthalic anhydride, methyl tetra/hexahydrophthalic anhydride, methyl nadic anhydride
● 固化反应机理：在无催化剂的情况下即使温度高达200℃，环氧基与酸酐的反应也很迟钝。酸酐通过与体系内的羟基反应来固化双酚A类环氧树脂，固化反应速度与羟基浓度成正比。
Curing reaction mechanism: In the absence of a catalyst, even if the temperature is as high as 200°C, the reaction between epoxy group and acid anhydride is very slow. The acid anhydride can react with hydroxyl group in the system for curing bisphenol A epoxy resin. The curing speed is proportional to the concentration of hydroxyl group.
S-186分子与四氢邻苯二甲酸酐反应必须在体系中加入催化剂。苯胺作为促进剂加入体系中可与酸酐发生酰基化反应，生成酰基衍生物和羧基。羧基可与环氧基发生反应生成仲醇，在体系内引入了羟基，从而达到加速反应目的。
A catalyst must be added into the system when S-186 reacts with tetrahydrophthalic anhydride. Aniline can be added into the system as an accelerator to react with acid anhydride to generate acyl derivatives and carboxyl groups. The carboxyl group can react with the epoxy group to form a secondary alcohol, and a hydroxyl group is introduced into the system to achieve the purpose of accelerating the reaction.
S-186树脂-胺类固化体系
S-186 resin and amine curing system
● 常用的胺类固化剂：脂肪胺，芳香族胺类固化剂（间苯二胺, 间苯二甲胺, 4,4-二氨基二苯基甲烷, DDS）
Commonly used amine curing agents: aliphatic amine, aromatic amine curing agent (m-phenylenediamine, m-xylylenediamine, 4,4-diaminodiphenylmethane, DDS)
●固化反应机理：常温下用脂肪胺冷固化。由于诱导效应，易受亲核试剂“胺类”的攻击，但S-186与脂肪胺的反应要比双酚A型温和很多。
Curing reaction mechanism: It is cold-cured with aliphatic amine at room temperature. Due to the induction effect, it is vulnerable to the attack of "amines" as nucleophiles, but the reaction of S-186 with aliphatic amines is much milder than that of bisphenol A type.
对于S-186/DDS体系按所确定的工艺制备浇注体，测其各项性能，同时与CYD-128/DDS体系作对比，从表中可以看出，S-186/DDS体系各项性能远高于CYD-128/DDS体系。
For the S-186/DDS system, prepare the pouring body according to the determined process and then test its various properties. At the same time, compare it with CYD-128/DDS system. It can be seen from the table that the performance of the S-186/DDS system is far higher than that of the CYD-128/DDS system.|
表1 S-186浇铸体性能 |
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性能 |
TDE-85/DDS |
CYD-128/DDS |
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拉伸强度/MPa |
62.2 |
52.4 |
|
拉伸模量/GPa |
4.3 |
2.85 |
|
断裂延伸率/% |
1.6 |
5.24 |
|
压缩强度/MPa |
203.3 |
128.2 |
|
弯曲强度/MPa |
113.3 |
81.51 |
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热变形温度/℃ |
214 |
139 |
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冲击强度/kJ·m-2 |
14.6 |
28.2 |
|
硬度/kg·mm-2 |
28.85 |
21.58 |
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线膨胀系数/℃-1 |
4.44x10-5 |
|
|
密度/g·cm-3 |
1.3107 |
1.23 |
S-186/DDS/S-GF（增强材料）复合材料性能
S-186/DDS/S-GF (reinforced material) composite material performance
研究结果表明，所制备的复合材料，其各项性能均比CYD-128/DDS/S-GF复合材料性能高，尤其是弯曲强度，提高了106%。
Some research results show that the composite material prepared has higher performance than CYD-128/DDS/S-GF composite material. Especially its bending strength is increased by 106%.|
表2 TDE-85/DDS/S-GF和CYD-128/DDS/S-GF复合材料性能对比 |
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性能 |
TDE-85/DDS/S-GF |
CYD-128/DDS/S-GF |
前者比后者提高的百分率/% |
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拉伸强度/MPa |
1276.4 |
1065.9 |
19.7 |
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拉伸模量/GPa |
58.1 |
42.3 |
37.4 |
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弯曲强度/MPa |
2008.1 |
974.3 |
106 |
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剪切强度/MPa |
114.5 |
86.1 |
33 |
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压缩强度/MPa |
1126.2 |
760.9 |
48 |
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纤维体积含量/% |
61.2 |
60.1 |
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碳纤维缠绕复合材料应用及发展前景
Application and development prospects of carbon fiber reinforced composites
碳纤维缠绕成型可充分发挥其高的比强度、比模量以及低密度的特点，可应用于压力容器、大型贮罐、高压管道、火箭发动机壳体等国防和民用领域。
Filament winding technology can give full play to its characteristics of high specific strength, high specific modulus and low density. It can be used in national defense and civil fields such as pressure vessels, large storage tanks, high-pressure pipelines, rocket engine shells, etc.
氢能是21世纪最有潜力的新型能源，具有高能、环保、可再生等优点,但氢气的储运技术滞后严重限制了其大规模应用。碳纤维缠绕复合材料氢气瓶因具有质量轻、韧性强、耐疲劳性好等优点，在储氢领域具有广阔的应用前景。
Hydrogen energy is the most promising new energy source in the 21st century. It has the advantages of high efficiency, environmental protection and renewable energy, but the lagging technology of hydrogen storage and transportation severely limits its large-scale application. The hydrogen cylinder which is made of carbon fiber reinforced composite has broad application prospects in the field of hydrogen storage, because it has advantages of light weight, strong toughness and good fatigue resistance.
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