水溶性芯模材料的制备与性能研究
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摘要
复合材料纤维缠绕成型工艺是将浸渍过树脂胶液的连续纤维(或布带、预浸纱)按照一定的规律缠绕到芯模上，然后经过固化、脱模获得制品的工艺过程。复合材料纤维缠绕成型工艺中有很多的产品不容易脱模，有些甚至无法脱模。本实验研究重点是用于缠绕成型的水溶性芯模材料，在缠绕成型后，在模具内注入一定温度的水，将模具溶解倒出，要求不影响缠绕的成品，强度达到1.5-2MPa，具有一定的表面光洁度，在缠绕过程及固化过程中要求芯模材料要保持尺寸的稳定。
本文首先综述了目前国内外水溶性高分子胶粘剂的各种改性利用方法及其在可溶芯上的应用现状，总结目前所存在的缺陷，然后提出了用改性淀粉及填料复合共混制备新型水溶性芯模高分子复合材料的新思路，在保持其力学性能基础之上提高芯模材料的水溶性。
目前，国内外对芯模材料的合成与利用上主要集中在石膏、水玻璃(盐芯)、陶瓷等无机粘结剂，聚乙二醇、聚乙烯醇、聚丙烯酸酯类等有机粘结剂的利用等方法。这些方法都在不同程度上存在着一定的缺陷。淀粉衍生物由于自身的结构特点，在共混成型过程中，可以实现保持其力学性能并提高芯模材料的水溶性。与此同时，淀粉衍生物的相容性好，在通过空心玻璃微珠进行增强后，能形成良好的界面结合。因此，采用空心玻璃微珠增强淀粉衍生物共混是一种新颖的值得探讨的方法。
本文以改性淀粉为基体，以空心玻璃微珠为填料，制备了水溶性芯模材料，并进行详细的实验研究。对水溶芯材料的结构与性能进行了剖析，探讨了其结构与性能间的相互关系，评价了水溶芯材料的力学性能与水溶性能。并采用经过优化了的水溶芯材料型芯工艺制造了玻璃纤维缠绕成型用芯模。结果显示，所制芯模材料有具有优良的力学性能及水溶性，能够缩短玻璃纤维缠绕生产成型周期并节约成本。
该水溶芯材料体系的结构是分散的固体颗粒相(空心玻璃微珠)与连续相(黄糊精、磷酸酯淀粉)结合良好的混合体。在常温下，这种混合体可通过常规的模压工艺成型为水溶芯材料。分散相粒子均匀分布在连续相内，这种结构赋予了其良好的水溶性能和力学性能。
对水溶芯材料配方进行了优化，目的是找到各方面性能均较为优越的水溶性型芯的配方及其制作方法。考虑了空心玻璃微珠、尿素、改性淀粉的含量对水溶芯材料综合性能的影响。
实验结果表明：加入一定量的尿素能够改善水溶芯材料的水溶性能，降低水溶芯材料的材料成本，获得综合性能较优的水溶芯材料。当空心玻璃微珠用量控制在10wt％时，水溶芯材料的综合性能更优；黄糊精、磷酸酯淀粉作为水溶芯材料体系的基体材料，其含量不能少于50wt％，否则水溶芯材料的成型将会变的非常困难。最佳配方为6wt％尿素，10wt％空心玻璃微珠及90wt％改性淀粉。
Fiber twist processing is an important technique with which contitinuous fiber(or cloth,pre-dipped yarn etc.)pre-dipped in ester emulsion is twisted around the core in turn,then solidizing, unloading to get the product. During this process,it is hard for many products to be unloaded,some even cannot be unloaded. This research is focused on the aqueous soluble core binder,the researchers prefer that after twisting process, filling in some water can solve the mold and get it out,which must not destroy the end-product,with compress sthength of 1.5-2MPa, fit surface smoothness, dimensional stability during twisting and solidizing.
The latest and recent research and developments of aqueous solubility adhesives (used for core binder of domestic and national) are described in this paper .The problems in the development of using technology for water-borne adhesives used in core binder were offered here, a new way is introduced here, using property-modified starch adhesion agent mixed with filler ,with which to make up the new type of aqueous core binder composite . A better aqueous property on the basis of keeping its mechanics property could be realized here.
It is used mainly on abio-adhesives such as plaster soluble glass and ceramic etc. and organic adhesives such as polyethylene alcohol、polyethylene glycol、polypropylene ester and so on home and abroad .These ways had some disfigurement in some degree. Duing to their configuration , the ramification of natural macromolecule can keep their mechanical property and improve their aqueous property. At the same time the ramification of natural macromolecule had good compatibility which can promote the interface combination. So it is possible to use the mixture of hollow glass-beads and the ramification of natural macromolecule.
The way of using modified starch as the matrix and hollow glass-beads as filler is investigated to make aqueous core binder. The correlation between its configuration and property was analysised and its aqueous property was estimated here. The samples are aqueous, showing good mechanical property. It proved fit for spaceflight fiberglass twist which can promote the manufacture of moulding.
The configuration of this aqueous core binder system was the fine-combined mixture which was made up of the dispersed solid grain (hollow glass-beads) and the continuous phase(modified starch).At the normal temperature,the mixture can be made by molding . The results show higher mechanical properties and aqueous solubility.
The composition was optimized in order to get a sample with best comprehesive properties. The content of the hollow glass-bead ,urea and starch was studied to find their influence on the composite.
The conclusion is: urea can improve composite's aqueous solubility and lower the manufaturing costs. While filling in 10%(wt) hollow glass-beads, sample appears better general properties. At the same time no less than 50%(wt )modified starch should be used as the matrix,otherwise the moulding must be very hard. The optimum is 6%(wt )urea, 10%(wt) hollow glass-beads and 90% (wt) modified starch.
本文首先综述了目前国内外水溶性高分子胶粘剂的各种改性利用方法及其在可溶芯上的应用现状，总结目前所存在的缺陷，然后提出了用改性淀粉及填料复合共混制备新型水溶性芯模高分子复合材料的新思路，在保持其力学性能基础之上提高芯模材料的水溶性。
目前，国内外对芯模材料的合成与利用上主要集中在石膏、水玻璃(盐芯)、陶瓷等无机粘结剂，聚乙二醇、聚乙烯醇、聚丙烯酸酯类等有机粘结剂的利用等方法。这些方法都在不同程度上存在着一定的缺陷。淀粉衍生物由于自身的结构特点，在共混成型过程中，可以实现保持其力学性能并提高芯模材料的水溶性。与此同时，淀粉衍生物的相容性好，在通过空心玻璃微珠进行增强后，能形成良好的界面结合。因此，采用空心玻璃微珠增强淀粉衍生物共混是一种新颖的值得探讨的方法。
本文以改性淀粉为基体，以空心玻璃微珠为填料，制备了水溶性芯模材料，并进行详细的实验研究。对水溶芯材料的结构与性能进行了剖析，探讨了其结构与性能间的相互关系，评价了水溶芯材料的力学性能与水溶性能。并采用经过优化了的水溶芯材料型芯工艺制造了玻璃纤维缠绕成型用芯模。结果显示，所制芯模材料有具有优良的力学性能及水溶性，能够缩短玻璃纤维缠绕生产成型周期并节约成本。
该水溶芯材料体系的结构是分散的固体颗粒相(空心玻璃微珠)与连续相(黄糊精、磷酸酯淀粉)结合良好的混合体。在常温下，这种混合体可通过常规的模压工艺成型为水溶芯材料。分散相粒子均匀分布在连续相内，这种结构赋予了其良好的水溶性能和力学性能。
对水溶芯材料配方进行了优化，目的是找到各方面性能均较为优越的水溶性型芯的配方及其制作方法。考虑了空心玻璃微珠、尿素、改性淀粉的含量对水溶芯材料综合性能的影响。
实验结果表明：加入一定量的尿素能够改善水溶芯材料的水溶性能，降低水溶芯材料的材料成本，获得综合性能较优的水溶芯材料。当空心玻璃微珠用量控制在10wt％时，水溶芯材料的综合性能更优；黄糊精、磷酸酯淀粉作为水溶芯材料体系的基体材料，其含量不能少于50wt％，否则水溶芯材料的成型将会变的非常困难。最佳配方为6wt％尿素，10wt％空心玻璃微珠及90wt％改性淀粉。
Fiber twist processing is an important technique with which contitinuous fiber(or cloth,pre-dipped yarn etc.)pre-dipped in ester emulsion is twisted around the core in turn,then solidizing, unloading to get the product. During this process,it is hard for many products to be unloaded,some even cannot be unloaded. This research is focused on the aqueous soluble core binder,the researchers prefer that after twisting process, filling in some water can solve the mold and get it out,which must not destroy the end-product,with compress sthength of 1.5-2MPa, fit surface smoothness, dimensional stability during twisting and solidizing.
The latest and recent research and developments of aqueous solubility adhesives (used for core binder of domestic and national) are described in this paper .The problems in the development of using technology for water-borne adhesives used in core binder were offered here, a new way is introduced here, using property-modified starch adhesion agent mixed with filler ,with which to make up the new type of aqueous core binder composite . A better aqueous property on the basis of keeping its mechanics property could be realized here.
It is used mainly on abio-adhesives such as plaster soluble glass and ceramic etc. and organic adhesives such as polyethylene alcohol、polyethylene glycol、polypropylene ester and so on home and abroad .These ways had some disfigurement in some degree. Duing to their configuration , the ramification of natural macromolecule can keep their mechanical property and improve their aqueous property. At the same time the ramification of natural macromolecule had good compatibility which can promote the interface combination. So it is possible to use the mixture of hollow glass-beads and the ramification of natural macromolecule.
The way of using modified starch as the matrix and hollow glass-beads as filler is investigated to make aqueous core binder. The correlation between its configuration and property was analysised and its aqueous property was estimated here. The samples are aqueous, showing good mechanical property. It proved fit for spaceflight fiberglass twist which can promote the manufacture of moulding.
The configuration of this aqueous core binder system was the fine-combined mixture which was made up of the dispersed solid grain (hollow glass-beads) and the continuous phase(modified starch).At the normal temperature,the mixture can be made by molding . The results show higher mechanical properties and aqueous solubility.
The composition was optimized in order to get a sample with best comprehesive properties. The content of the hollow glass-bead ,urea and starch was studied to find their influence on the composite.
The conclusion is: urea can improve composite's aqueous solubility and lower the manufaturing costs. While filling in 10%(wt) hollow glass-beads, sample appears better general properties. At the same time no less than 50%(wt )modified starch should be used as the matrix,otherwise the moulding must be very hard. The optimum is 6%(wt )urea, 10%(wt) hollow glass-beads and 90% (wt) modified starch.
引文
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(5)陈宗雨，郭伟，曾建民．精密铸造可溶性石膏芯的研究．航空精密制造技术．2002，38(3)：25-28
(6)罗继相．耐高压易溶芯的研制与应用．铸造，2002，51(2)：92-95
(7)阂小俊，李宁，何益明．精密铸造磷酸盐粘结自硬型芯的试验研究．特种铸造及有色合金，2005，25(7)：428-430n
(8)严瑞碹．水溶性高分子．北京：化学工业出版社，1998
(9)L Yu, G Christie. Microstructure and Mechanical Properties of Orientated Thermoplastic Starches. Journal of Materials Science,2004,(40): 111-116
(10)Long Yu, Gregore Christie. Measurement of Starch Thermal Transitions Using Scanning Calorimetry. Carbohydrate Polymers,2001,(46): 179-184
(11)汪多仁．木薯淀粉粘合剂的制造与应用．中国胶粘剂．2003，12(3)：62-63
(12)周霞等．α淀粉复合胶粘剂在型砂中的应用研究．铸造技术，1996，(4)：44-48
(13)边风刚，李国禄，刘金海．β淀粉用作芯砂主粘结剂的研究．材料与表面处理，2002，(2)：43-45
(14)张辉，姜文勇．砂型用改性普通玉米淀粉粘结剂的研究．应用能源技术，2000，(3)：10-11
(15)张俐娜．天然高分子改性材料及应用．北京：化学工业出版社，2005
(16)OB WURZBURG. Modified starches:properties and uses.CRC Press INC. BOCA Raton,Flarida, USA, 1987
(17)宫泽信夫．淀粉型砂加热铸型中淀粉的移动和加热铸型的性质．铸造，1986，58(9)：647-652
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