玻璃纤维增强光固化树脂基复合材料的制备及性能研究
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摘要
本实验采用可见光固化技术制备了两种丙烯酸类高聚物，经过反复试验，确定了基体单体优选配比。同时将可见光固化技术与传统复合材料制备方法相结合，以玻璃纤维作为增强体制备出玻璃纤维增强树脂基复合材料，并对其力学性能、摩擦磨损性能及体积收缩等情况进行了研究；利用扫描电镜（SEM）及差热扫描量热仪(DSC)等测试手段对各类断口、磨损面及材料的热性能进行了分析。
研究结果表明，将光固化技术用于制备玻璃纤维增强树脂基复合材料是完全可能的；纤维的加入可有效提高树脂材料的各项力学性能，同时随着纤维体积含量的提高，力学性能也呈上升趋势；玻璃纤维偶联处理能有效改善纤维与树脂基体之间的结合，从而提高复合材料的力学性能。
对于EEPE及其GL/EEPE复合材料，引发剂含量和纤维体积分数对材料加热过程中焓变最剧烈时所对应的温度T2无明显影响。单体含量能够影响材料的起始热变形温度，对T2无明显影响。
磨损条件对材料的耐磨性能影响较大。模拟体液润滑可有效降低材料的磨损率。同时纤维的加入可有效提高材料的耐磨性；在模拟体液润滑条件下，三维编织纤维增强复合材料的耐磨性较好；同时载荷及滑动速度对材料的耐磨性也有一定的影响。
与其他甲基丙烯酸类树脂相比，EEPE树脂的聚合收缩率比较低。相同纤维体积分数的GL/EEPE复合材料与G3D/EEPE复合材料固化收缩率相差不大。
本实验结合了光固化技术与复合材料的优势，制备工艺简单，材料性能好，能够基本克服传统骨折外固定材料，如小夹板及石膏等的固有缺点，为新型骨折外固定材料提供了一个发展方向。但是今后对光固化机理、光固化质量影响因素及实际应用等方面的研究还需要进一步深入。
Two kinds of dimethacrylate resin were prepared using visible light-cured technique. Optimal proportion of several monomers was conformed through reduplicate examination. The light-cured resin matrix composites were prepared with dimethacrylate oligomers as monomers, camphorquinone (CQ) and benzoate as photoinitiators, and glass fiber as reinforced materials. Mechanical property, friction and wear characteristics and polymerization volume shrinkage of them were investigated. Friction and wear surfaces and thermodynamics of the materials were analyzed with SEM and DSC.
The result showed that it is possible to prepare glass fiber reinforced composites with light-cured technology. Mechanical property of resin materials could be effectively improved because of incorporation of fiber. At the same time the main mechanical properties were improved effectively with the increase of fiber volume. The conjointness between glass fiber and resin was effectively improved through coupling- agent surface treatment, so the performance of composites was improved. As for EEPE and GL/EEPE composites, photoinitiator and monomer content and fiber volume had no obvious effect on the temperature T2 at which the enthalpy of transformation of polymer was the most acute in course of heating.
Wear condition had obvious effect on the wear-resistant of materials. The friction coefficient of dry-friction was higher than that of the friction under simulative body-lubrication．Wear rate can be reduced by incorporation of glass fiber, and the friction and wear properties of 3D-braided fiber reinforced composites were best among 3D-braided fiber reinforced composites, continuous fiber reinforced composites and resin matrix. Load and glide velocity had effect on friction and wear behavior of composites.
Polymerization volume shrinkage of EEPE resin was lower than other dimethacrylate resin. The polymerization volume shrinkage of GL/EEPE composites and G3D/EEPE composites was almost close, but was higher than that of EEPE resin. At the same time volume shrinkage was reduced with the increase of fiber volume.
Fiber reinforced light-cured resin matrix composites unite many characters of light-cured technology and composites。The preparation technics of the materials is very easy and mechanical properties of them are good. They can overcome the connatural shortcoming of traditional fracture exterior fixation materials, such as plywood and plaster cast, so they offer a new development direction for fracture exterior fixation materials. But study on light-cured reaction mechanism, functionality and actual application etc will be researched in the future.
研究结果表明，将光固化技术用于制备玻璃纤维增强树脂基复合材料是完全可能的；纤维的加入可有效提高树脂材料的各项力学性能，同时随着纤维体积含量的提高，力学性能也呈上升趋势；玻璃纤维偶联处理能有效改善纤维与树脂基体之间的结合，从而提高复合材料的力学性能。
对于EEPE及其GL/EEPE复合材料，引发剂含量和纤维体积分数对材料加热过程中焓变最剧烈时所对应的温度T2无明显影响。单体含量能够影响材料的起始热变形温度，对T2无明显影响。
磨损条件对材料的耐磨性能影响较大。模拟体液润滑可有效降低材料的磨损率。同时纤维的加入可有效提高材料的耐磨性；在模拟体液润滑条件下，三维编织纤维增强复合材料的耐磨性较好；同时载荷及滑动速度对材料的耐磨性也有一定的影响。
与其他甲基丙烯酸类树脂相比，EEPE树脂的聚合收缩率比较低。相同纤维体积分数的GL/EEPE复合材料与G3D/EEPE复合材料固化收缩率相差不大。
本实验结合了光固化技术与复合材料的优势，制备工艺简单，材料性能好，能够基本克服传统骨折外固定材料，如小夹板及石膏等的固有缺点，为新型骨折外固定材料提供了一个发展方向。但是今后对光固化机理、光固化质量影响因素及实际应用等方面的研究还需要进一步深入。
Two kinds of dimethacrylate resin were prepared using visible light-cured technique. Optimal proportion of several monomers was conformed through reduplicate examination. The light-cured resin matrix composites were prepared with dimethacrylate oligomers as monomers, camphorquinone (CQ) and benzoate as photoinitiators, and glass fiber as reinforced materials. Mechanical property, friction and wear characteristics and polymerization volume shrinkage of them were investigated. Friction and wear surfaces and thermodynamics of the materials were analyzed with SEM and DSC.
The result showed that it is possible to prepare glass fiber reinforced composites with light-cured technology. Mechanical property of resin materials could be effectively improved because of incorporation of fiber. At the same time the main mechanical properties were improved effectively with the increase of fiber volume. The conjointness between glass fiber and resin was effectively improved through coupling- agent surface treatment, so the performance of composites was improved. As for EEPE and GL/EEPE composites, photoinitiator and monomer content and fiber volume had no obvious effect on the temperature T2 at which the enthalpy of transformation of polymer was the most acute in course of heating.
Wear condition had obvious effect on the wear-resistant of materials. The friction coefficient of dry-friction was higher than that of the friction under simulative body-lubrication．Wear rate can be reduced by incorporation of glass fiber, and the friction and wear properties of 3D-braided fiber reinforced composites were best among 3D-braided fiber reinforced composites, continuous fiber reinforced composites and resin matrix. Load and glide velocity had effect on friction and wear behavior of composites.
Polymerization volume shrinkage of EEPE resin was lower than other dimethacrylate resin. The polymerization volume shrinkage of GL/EEPE composites and G3D/EEPE composites was almost close, but was higher than that of EEPE resin. At the same time volume shrinkage was reduced with the increase of fiber volume.
Fiber reinforced light-cured resin matrix composites unite many characters of light-cured technology and composites。The preparation technics of the materials is very easy and mechanical properties of them are good. They can overcome the connatural shortcoming of traditional fracture exterior fixation materials, such as plywood and plaster cast, so they offer a new development direction for fracture exterior fixation materials. But study on light-cured reaction mechanism, functionality and actual application etc will be researched in the future.
引文
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[3] 凌强,朱建民著.实用骨折固定手册[M].江西:江西科学技术出版社,1999:1～2
[4] 郭振河,郑晓明,杨家辉等. 交锁髓内钉在下肢长骨骨折中的应用[J]. 临床医药杂志(Journal of Clinical Medicine and Pharmacy).2003,16(1):31～33
[5] 张丽,李红芳.CoUes骨折小夹板外固定的健康教育[J].中医正骨.2002,15(3):31
[6] 张元民,王志彬,李文成.新型塑质夹板的力学性能测试和分析[J].中国骨伤.2002,15(8):473～474
[7] 袁鸿宾,姚武.热塑外固定材料的物理力学测试[J].中国矫形外科杂志.1999,6(4):311
[8] 陈慧敏,金伟兰.新型医用外固定材料---PCL型塑性夹板[J].1992,1:1～4
[9] 石光越,李志挺,袁旭有等. 组合式骨外固定架在骨科临床的应用[J].中国煤炭工业医学杂志.2003,6(4):356
[10] 赵杰,张兴胜,刘瑞智等.组合式外固定架超关节固定治疗Pilon骨折[J].实用骨科杂志.2003,9(1):54～55
[11] 付三清,夏万平,谌思萍.组合外固定治疗不稳定性胚排骨骨折[J].中国现代医学杂志.2002,12(8):89～90
[12] 杨永源,吴玉民,胡辉等.辐射固化材料的现状和某些发[J].感光科学与光化学.2002,3:31～35
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[15] 万小龙.光固化树脂体系及其应用[J].黎明化工.1994,1:19～24
[16] 王素琴,曹瑞军,段玉岗.光固化树脂的制备及应用[J].化学工程.1999,27:44～46
[17] Timothy F S,Wayne D C,John S F.Photo～DSC cure kinetics of vinyl ester resins.I.Influence of temperature[J].Polymer.2002,43:5839～5845
[18] 李善君,纪才圭,李橦等.高分子光化学原理及应用[M].上海:复旦大学出版社.1993,108
[19] 王素琴,曹瑞军,段玉岗.光固化树脂的制备及应用[J].化学工程.1999(27):44～46
[20] 郑耀臣,魏无际.光固化涂料用光引发剂的进展[J].涂料工业.2002(1):31～35
[21] C.G.罗菲著,黄毓礼等译.光聚合高分子材料及应用[M].北京:科学技术文献出
版社.1990:93
[22] Sumiyoshi T et al.On the photolysis of acylphosphine oxides:1.laser flash photolysis studied with 2,4,6-trimethylbenzoyldiphenylphosphine oxide [J]. Polymer.1985(26):141～146
[23] Jeffrey W.Stansbury,Sabine H.Dickens.Network formation and compositional drift during photo-initiated copolymerization of dimethacrylate monomers [J].polymer. 2001(42):6363～6369
[24] Wang G, Culbertson BM, Xie D,Seghi RR.Effect of fluorinated trithylede glycol dimethylate on the propertied of unfilled.light cured dental resins[J].J Macromol SciPure Appl Chen1999;36:237～52
[25] 秦长喜,刘瀛.辐射固化材料的市场及发展[J].信息记录材料.2003,3(1):36～41
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