CN111501345B - 一种柔性加固复合材料及其制备方法 - Google Patents

一种柔性加固复合材料及其制备方法 Download PDF

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CN111501345B
CN111501345B CN202010332451.0A CN202010332451A CN111501345B CN 111501345 B CN111501345 B CN 111501345B CN 202010332451 A CN202010332451 A CN 202010332451A CN 111501345 B CN111501345 B CN 111501345B
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composite material
reinforced composite
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woven fabric
spraying
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CN111501345A (zh
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张典堂
梁琦
钱坤
徐阳
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Jiangnan University
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Abstract

本发明公开了一种柔性加固复合材料及其制备方法，属于防护工程技术领域。本发明所述的柔性加固复合材料的制备方法，包括以下步骤：将机织物在浆料浸轧液中浸渍、干燥得到预处理的机织物；随后利用喷涂聚脲弹性体技术在预处理的机织物的表面喷涂聚脲涂层，即得到柔性加固复合材料；其中浆料浸轧液的组分包括马铃薯淀粉、玉米原淀粉、水性聚氨酯。本发明制备得到的柔性加固复合材料可以对钢筋混凝土类材料加固，具有柔性、大面积曲面覆盖、重量轻、便于储存运输、适用范围广、快速加固抢修、抗爆与抗侵彻性能好等优点，更适合拱桥等特殊结构的抗爆加固。

Description

一种柔性加固复合材料及其制备方法
技术领域
本发明涉及一种柔性加固复合材料及其制备方法，属于防护工程技术领域。
背景技术
防护工程是一个国家人民生命和财产的安全保障，更体现了一个国家在面对战争时所具备的基本防御能力，可以说防护工程的建设，事关国家的生死存亡。随着现代先进武器如精确制导武器、钻地武器的发展，这些武器获得了更强的破坏能力，而防护工程的升级换代也需要紧跟时代的步伐。
对于目前军事防护工程，主要针对阵地工程，一旦遭受到导弹爆炸侵彻袭击，会对工程结构造成严重破坏，严重威胁人员及物资设备的安全。目前常用的材料以混凝土或钢筋混凝土为主，存在重量大、防护效果差、维护困难、无法进行快速抢修等缺陷。
发明内容
为了解决上述至少一个问题，本发明将高性能纤维混杂设计应用在机织物中，将制备好的机织物经马铃薯淀粉、玉米原淀粉、水性聚氨酯乳液共混浆料浸渍，采用一浸一轧法，干燥得到预处理的机织物；随后利用喷涂弹性体技术在预处理的机织物表面喷涂聚脲涂层，得到柔性加固复合材料。对于军事防护阵地工程中的混凝土与钢筋混凝土，可以利用本发明的复合材料对其表面进行加固，以实现快速构筑、加固抢修、大面积防护、而且可以协助提升其抗爆和抗侵彻能力，提高抗震塌能力，实现安全保障和快速响应的需求；如防护工程中的拱桥，利用本发明的复合材料可快速对受损的拱桥抗震塌加固，与拱桥紧密、牢固粘合的同时实现大面积有效防护，提高抗爆炸与抗侵彻能力。此外，本发明利用胶粘剂，将制备好的柔性加固复合材料与混凝土类材料牢固的粘结，且满足《工程结构加固材料安全性鉴定技术规范》加固标准。
本发明的第一个目的是提供一种柔性加固复合材料的制备方法，包括以下步骤：
将机织物在浆料浸轧液中浸渍、干燥得到预处理的机织物；随后利用喷涂聚脲弹性体技术在预处理的机织物的表面喷涂聚脲涂层，即得到柔性加固复合材料；其中浆料浸轧液的组分包括马铃薯淀粉、玉米原淀粉、水性聚氨酯。
在本发明的一种实施方式中，所述浆料浸轧液的制备方法为：将玉米原淀粉、马铃薯淀粉、水性聚氨酯乳液按照50:(6-10):(2-8)的比例进行共混。
在本发明的一种实施方式中，所述水性聚氨酯乳液的含固量为10-20％，也就是水性聚氨酯乳液中水性聚氨酯的量为10-20％。
在本发明的一种实施方式中，所述水性聚氨酯乳液的含固量为15％。
在本发明的一种实施方式中，所述浆料浸轧液的制备方法为：将玉米原淀粉、马铃薯淀粉、水性聚氨酯乳液按照50:8:6的比例进行共混。
在本发明的一种实施方式中，所述的浸渍具体为：采用一浸一轧法将机织物在浆料浸轧液中浸渍，随后在室温下通风处静置晾干；带液率(轧余率)为50-55％。
在本发明的一种实施方式中，所述的玉米原淀粉由邳州奋达淀粉有限公司生产。
在本发明的一种实施方式中，所述的聚脲原料选用LINE-X公司的line-xs-350，聚脲是由异氰酸酯和二胺低聚物的共聚反应形成的，其密度为1.08g/cm3，弹性模量为200MPa，抗拉强度为22.40MPa。
在本发明的一种实施方式中，所述的喷涂聚脲的步骤为：利用喷涂设备在预处理的机织物表面喷涂聚脲；其中所述的聚脲为异氰酸酯和二胺低聚物两组分按照混合体积比为1:1混合均匀得到，喷涂压力为55～65MPa，喷涂温度为55～70℃。高压喷涂设备为Reactor H-XP3主机及Fusion的AP枪。
在本发明的一种实施方式中，所述的机织物表面为机织物的正面或背面，即机织物面积最大的那个面。
在本发明的一种实施方式中，所述的喷涂聚脲的厚度为1-4mm。
在本发明的一种实施方式中，按照公知文献(周建,范浩军,陈试伟,可生物降解水性聚氨酯浆料的合成和性能研究[J].棉纺织技术,2011,039(010):9-12.)的方法制备水性聚氨酯乳液，制得含固量为5-20％的水性聚氨酯乳液，具体步骤为：将PBA2000、PEA2000、PPG3000真空干燥脱水后倒入装有氮气冷凝回流管、机械搅拌器、温度计的四口烧瓶中，低温加入IPDI，滴加少量催化剂，升温至75～80℃，反应2h-3h后，降温到55℃后用加入DMF溶解的DMPA进行扩链，测其-NCO到理论值后，加入少量丙酮调节黏度；经三乙胺中和后，在快速搅拌条件下加入去离子水，并用减压蒸馏方法去除溶剂，得到稳定的水性聚氨酯乳液。
在本发明的一种实施方式中，所述的机织物是高强聚乙烯纤维、碳纤维、芳纶纤维中的一种或两种以上的纤维采用机织工艺制备得到。
在本发明的一种实施方式中，所述的机织物是采用三维正交、层层角联锁、多层缝合、贯厚度角联锁中的任意一种或两种以上的方式制得。
在本发明的一种实施方式中，所述的机织物为三维正交机织物。
在本发明的一种实施方式中，所述机织物为三维正交机织物，是在改造过的传统剑杆织机上织得的多层正交机织物；选用的接结组织为经纱结节，用这种方法制备得到的三维正交机织物具有良好的力学承载性能。
在本发明的一种实施方式中，所述的三维正交机织物中选用东丽公司T620SC-24K-50C碳纤维，线密度为1850tex；日本帝人公司的芳纶(3220dtex/2000f)纤维；荷兰DSM公司的DyneemSK-66。
在本发明的一种实施方式中，所述的柔性加固复合材料柔软性能优异，可卷曲，幅宽≥1m，长度≥20m，厚度在2mm～50mm之间，优势在于其覆盖面积大，快速抢修，曲面覆盖，可以协助提升抗爆和抗侵彻能力，更好的满足在爆炸过程中的高效防护要求，适用性更强。
在本发明的一种实施方式中，所述的三维正交机织物制备过程中经纱层数为6层，纬纱层数为7层，机织物厚度为6mm，宽度为1.5m，长度为20m。
本发明的第二个目的是本发明用所述的一种柔性加固复合材料的制备方法得到的柔性加固复合材料。
本发明的第三个目的是本发明所述的柔性加固复合材料在表面加固混凝土类材料中的应用。
在本发明的一种实施方式中，包括如下步骤：采用胶粘剂将本发明所述的柔性加固复合材料与混凝土类材料牢固的粘合在一起，胶粘剂的厚度为1-3mm，得到用于混凝土类材料表面加固的多层复合材料。
在本发明的一种实施方式中，所述的胶粘剂为山东大工复合材料有限公司的T1胶粘剂。
本发明的第四个目的是本发明的方法得到的表面加固混凝土类材料。
本发明的第五个目的是本发明所述的柔性加固复合材料在拱桥加固中的应用。
在本发明的一种实施方式中，具体应用为：在拱桥的外表面，利用山东大工复合材料有限公司的T1胶粘剂将本发明的柔性加固复合材料与拱桥牢固的粘合在一起，胶粘剂的厚度为2mm；所述柔性加固复合材料包括聚脲层和机织物，其中，聚脲层作为迎爆面。
在本发明的一种实施方式中，将本发明所述的柔性加固复合材料用于拱桥可以实现防护的高效、轻质、大面积、快速加固和抢修等特征，协助提升抗爆和抗侵彻能力，实现安全保障和快速响应的需求。
在本发明的一种实施方式中，将柔性加固复合材料用于防护工程中拱桥形结构的外表面，利用胶粘剂将本发明的柔性加固复合材料牢固的粘贴在拱桥的外表面；如果防护要求较高时，可将多个本发明的柔性加固复合材料堆叠粘合在拱桥的外表面，减少拱桥的局部震塌破坏与爆炸破坏；胶黏剂选用山东大工复合材料有限公司的T1胶黏剂，胶粘剂的厚度为2mm。
本发明的技术效果如下：
(1)本发明可以协助提升抗爆和抗侵彻能力，提高抗爆炸震塌能力，防护效果好，可以满足抗破片侵彻GJB4300A-2012Ⅱ级以上。
(2)本发明通过混合浆料浸轧液浸渍机织物可提高织物的力学性能，达到类似剪切增稠的效果增强聚脲涂层与机织物间的粘结强度，同时有利于均匀平整的喷涂聚脲。
(3)利用本发明的复合材料进行加固，优势在于加固材料是柔性的、可卷曲、可实现大面积覆盖、能应用在拱桥等特殊结构，与材料表面充分接触进行曲面覆盖，对于拱桥等特殊结构的抗爆加固更有效。
(4)在日常的储藏、运输过程中，本发明是柔性的，可卷曲起来便以使用；同时其质地轻、便于携带运输，适用性强且适用范围广，能在某些复杂条件下使用。
(5)与其它加固方法、加固材料相比，本发明质量轻、使用简单方便、防护面积大、抗爆与抗侵彻性能好、可进行快速抢修加固以满足高效、快速防护的需求，具有较高的附加值。
附图说明
图1是柔性加固复合材料的结构示意图，结构1是聚脲涂层，结构2是混合浆料浸轧液浸渍预处理后的三维正交机织物。
图2是三维正交机织物的正面效果图。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。
破片加载试验：利用口径为12.7mm的滑膛弹道枪对涂覆了聚脲涂层的经混合浆料浸轧液浸渍的柔性加固复合材料进行不同速度范围的冲击侵彻实验，高速冲击发数为六发，通过测定弹道极限速度，分析柔性加固复合材料抗冲击性能。
拉伸性实验：根据中国国家标准《GB/T7685.1-2001增强材料机织物试验方法》，在电子万能材料试验机上，对混合浆料浸轧液浸渍的机织物拉伸性进行测试，依据测得的拉伸强度表征柔韧性及抗冲击性。
刚柔性测试：参照日本工业标准JIS-L1096的B法测定试样的刚柔性，通过公式
Figure BDA0002465445520000041
计算刚度；
刚度越小，柔韧性越好；式中，B为材料的刚度/(N·cm)；δ为试验片的弯曲长度/cm；W——试验片单位面积的重量/(N·cm-2)；L——试验片的被测试长度/cm。
实施例1
一种柔性加固复合材料，如图1所示，所述的柔性加固复合材料包含机织物表面的聚脲涂层1，混合浆料浸轧液浸渍后的三维正交机织物2；三维正交机织物厚度为6mm，长度达20m，宽度为1.5m；纬纱为东丽公司T620SC-24K-50C碳纤维，线密度为1850tex；经纱为日本帝人公司的芳纶(3220dtex/2000f)纤维，Z向纱为荷兰DSM公司的DyneemSK-66；将6层经纱呈现伸直状态穿过改进过的织机，用7根纬纱喂入经纱间的空隙，利用综丝上下运动来对Z向纱实施固定。
三维正交机织物的正面效果图如图2所示。三维正交机织物的经密、纬密分别为55根/10cm、46根/10cm，测得的刚度为0.96，经向平均最大断裂强力5.748N，纬向平均最大断裂强力4.854N，经向平均拉伸强度为208.159MPa，纬向平均拉伸强度为176.285MPa。
所述的柔性加固复合材料的制备方法，包括以下步骤：
(1)共混浆料浸轧液的制备：
按照文献(周建,范浩军,陈试伟,可生物降解水性聚氨酯浆料的合成和性能研究[J].棉纺织技术,2011,039(010):9-12.)的方法制备水性聚氨酯乳液，制得含固量为15％的水性聚氨酯乳液。具体方法为将PBA2000、PEA2000、PPG3000真空干燥脱水后倒入装有氮气冷凝回流管、机械搅拌器、温度计的四口烧瓶中，低温加入IPDI，滴加少量催化剂，升温至75～80℃，反应2h一3h后，降温到55℃后用加入DMF溶解的DMPA进行扩链，测其一Nc0到理论值后，加入少量丙酮调节黏度。经三乙胺中和后，在快速搅拌条件下加入去离子水，并用减压蒸馏方法去除溶剂，得到稳定的水性聚氨酯乳液。
将50kg的玉米原淀粉、8kg马铃薯淀粉、6kg含固量为15％的水性聚氨酯乳液、450L水混合配置成混合浆液，得到共混浆料浸轧液。
(2)预处理的机织物的制备：采用一浸一轧法将三维正交机织物在步骤(1)制备得到的共混浆料浸轧液中浸渍，轧余率为55％，随后在室温下通风处静置晾干后，得到预处理的三维正交机织物。
(3)柔性加固复合材料的制备：
聚脲选用LINE-X公司的line-xs-350，利用高压喷涂设备在预处理的机织物表面喷涂聚脲，其中聚脲是由异氰酸酯和二胺低聚物两组分混合均匀得到的，混合体积比为1:1。高压喷涂设备为Reactor H-XP3主机、Fusion的AP枪和T-2型气动抽料泵。利用AP枪在预处理的三维正交机织物表面喷涂3mm厚的聚脲涂层，喷涂时的最佳喷涂压力为55～65MPa，喷涂温度为55～70℃。
性能测试：依据以上的步骤制备的柔性加固复合材料，可以防住5m外12.7mm口径线膛弹道枪的破片侵彻。参照《GJB4300A-2012军用防弹衣安全技术性能要求》标准，可以满足破片侵彻GJB4300A-2012Ⅱ级以上。
实施例2
参照实施例1，将马铃薯淀粉的用量分别替换为2kg，4kg，6kg，10kg，其他条件不变，制备得到预处理的机织物，再与聚脲复合得到柔性加固复合材料。具体测试结果见表1、表2、表3；表1为不同马铃薯淀粉用量预处理的机织物的拉伸性能结果；表2为不同马铃薯淀粉用量制备的柔性加固复合材料侵彻性能结果；表3为不同马铃薯淀粉用量下的柔性加固复合材料刚柔性结果。
表1不同马铃薯淀粉用量预处理的机织物的拉伸性能结果
Figure BDA0002465445520000061
表2不同马铃薯淀粉用量制备得柔性加固复合材料侵彻性能结果
Figure BDA0002465445520000062
表3不同马铃薯淀粉用量下的柔性加固复合材料刚柔性结果
马铃薯淀粉用量(kg) 2 4 6 10
刚度 1.06 1.09 1.13 1.23
从表1可以看出，随着马铃薯淀粉用量的增加，浸渍后的织物拉伸性增强，但当马铃薯淀粉的用量增加至10kg时，与实施例1相比，拉伸性减弱。从表2可以看出，随着马铃薯淀粉用量的增加，柔性增强加固材料抗侵彻性增强，用量达到10kg时，与实施例1相比，弹道极限速度减小。从表3可以看出，马铃薯淀粉会增强柔性增强加固材料的刚性。
实施例3
参照实施例1，将水性聚氨酯乳液的含固量分别改为5％、10％、20％，30％，其他条件不变，制备柔性加固复合材料。具体结果见表4、表5。
表4不同水性聚氨酯乳液的含固量预处理的机织物拉伸性能结果
Figure BDA0002465445520000071
表5不同水性聚氨酯乳液的含固量制备的柔性加固复合材料侵彻性能结果
Figure BDA0002465445520000072
表6不同水性聚氨酯乳液的含固量制备的柔性加固复合材料刚柔性结果
Figure BDA0002465445520000073
从表4可以看出，随着水性聚氨酯乳液含固量的增加，浸渍后的织物拉伸性增强，但当水性聚氨酯乳液含固量增加至20％时，拉伸性减弱，当含固量达到30％时，拉伸性明显变差。从表5可以看出，随着水性聚氨酯乳液含固量增加，柔性增强加固材料抗侵彻性增强，含固量为15％时，弹道极限速度最大，含固量进一步增加会使弹道极限速度下降。从表6可以看出，水性聚氨酯乳液的含固量会使柔性增强加固材料的柔性增强。综合各项性能水性聚氨酯的含固量最好为10％～20％。
实施例4
调整三维正交机织物的厚度为3mm，其他参数和实施例1保持一致，得到柔性加固复合材料。
利用山东大工复合材料有限公司的T1胶粘剂将柔性加固复合材料牢固的粘贴在混凝土表面，聚脲层作为迎爆面，协助提高其抗爆与抗侵彻能力，符合《工程结构加固材料安全性鉴定技术规范》标准。在爆炸测试场进行试验，将1KgTNT距离粘贴柔性增强加固材料的混凝土0.5m引爆，混凝土不会发生坍塌。而将柔性增强加固材料撤去，在相同距离引爆1kgTNT，混凝土出现明显的坍塌现象。
表7实施例1、4中经预处理的机织物拉伸性能结果
Figure BDA0002465445520000081
表8实施例1、4制备得柔性加固复合材料侵彻性能结果
Figure BDA0002465445520000082
表9实施例1、4制备的柔性加固复合材料刚柔性结果
实施例 刚度
1 1.17
4 1.08
从表7、表8、表9可以看出，本发明的综合性能是较好的。且将机织物的厚度改为3mm时，也具有较好的防护效果。从表8可以看出，实施例1的弹道极限速度最大，抗侵彻性相对较好。从表9可以看出，织物厚度的减少，使得柔性增强加固材料获得了更好的柔性。
实施例5
利用本发明对拱桥类结构加固是十分有利的，采用和实施例1相同的方法制备柔性增强加固材料。利用山东大工复合材料有限公司的T1胶粘剂将柔性增强加固材料与拱桥牢固的粘合在一起，胶粘剂的厚度为2mm。聚脲层作为迎爆面使用，协助提高拱桥形结构的抗爆与抗侵彻能力，加固过程符合《工程结构加固材料安全性鉴定技术规范》标准。
对照例1
参照实施例1，在合成水性聚氨酯乳液的过程中，将降温至55℃改为降温至65℃，制得柔性加固复合材料。
对照例2
将实施例1的聚脲涂层改为预处理的织物两面全面积喷涂，喷涂聚脲的厚度及其他参数和实施例1保持一致，得到柔性加固复合材料。
对照例3
将实施例1的共混浆料调整为50kg的玉米原淀粉、6kg水性聚氨酯乳液，不使用马铃薯淀粉，其他参数和实施例1保持一致，得到柔性加固复合材料。
对照例4
将实施例1的共混浆料调整为6kg水性聚氨酯乳液、8kg马铃薯淀粉、不使用玉米原淀粉，其他参数和实施例1保持一致，得到柔性加固复合材料。
对照例5
将实施例1的共混浆料调整为30kg的玉米原淀粉、10kg马铃薯淀粉、8kg水性聚氨酯乳液，其他参数和实施例1保持一致，得到柔性加固复合材料。
对照例6
将实施例1聚脲喷涂时的压力修改为70Mpa，其他参数和实施例1保持一致，得到柔性加固复合材料。
对照例7
将实施例1的聚脲的喷涂厚度改为10mm，其他参数和实施例1保持一致，得到柔性加固复合材料。
对照例8
省略机织物的预处理步骤，直接对实施例1的机织物喷涂聚脲，参数和实施例1保持一致，得到柔性加固复合材料。
表10对照例的柔性加固复合材料侵彻性能结果
Figure BDA0002465445520000101
表11对照例中经预处理后的机织物拉伸性能结果
Figure BDA0002465445520000102
表12对照例柔性加固复合材料的刚柔性结果
实验结果 对照例1 对照例2 对照例3 对照例4 对照例5 对照例6 对照例7 对照例8
刚度 1.21 1.30 1.09 1.07 1.32 1.28 1.39 1.03
从表10中可以看出，当调整水性聚氨酯乳液的温度、喷涂聚脲的压力、聚脲喷涂的策略、共混浆料的配比时，它们所对应的弹道极限速度均减小，抗侵彻能力均减弱。当增加聚脲涂层的厚度时，弹道极限速度增大，但刚度增加，柔性减弱，适用性变差。从表11中可以看出，当调整水性聚氨酯乳液的温度、共混浆料的配比时，平均最大断裂强力、平均拉伸强度均减小。通过对比例可以看出，本发明的参数选取是有一定范围限制的，利用本发明的方法任意选取参数得到的柔性加固材料无法达到理想的效果。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (8)

1.一种柔性加固复合材料的制备方法，其特征在于，包括以下步骤：将机织物在浆料浸轧液中浸渍、干燥得到预处理的机织物；随后在预处理的机织物的表面喷涂聚脲涂层，即得到柔性加固复合材料；
其中浆料浸轧液的组分包括马铃薯淀粉、玉米原淀粉、水性聚氨酯；所述浆料浸轧液的制备方法为：将玉米原淀粉、马铃薯淀粉、水性聚氨酯乳液按照50:(6-10):(2-8)的比例进行共混；
所述水性聚氨酯乳液的含固量为10-20％；
所述的聚脲涂层为异氰酸酯和二胺低聚物两组分按照混合体积比为1:1混合均匀得到。
2.根据权利要求1所述的制备方法，其特征在于，所述的喷涂聚脲的步骤为：利用喷涂设备在预处理的机织物表面喷涂聚脲；其中，喷涂压力为55～65MPa，喷涂温度为55～70℃。
3.根据权利要求1或2所述的制备方法，其特征在于，所述的机织物是通过三维正交、层层角联锁、多层缝合、贯厚度角联锁中的任意一种或两种以上的方式制得。
4.权利要求1-3任一项所述的制备方法得到的柔性加固复合材料。
5.权利要求4所述的柔性加固复合材料在表面加固混凝土类材料中的应用，其特征在于，采用胶粘剂将权利要求4所述的柔性加固复合材料与混凝土类材料牢固的粘合，胶粘剂的厚度为1-3mm。
6.权利要求5所述的方法得到的表面加固混凝土类材料。
7.权利要求4所述的柔性加固复合材料在拱桥加固中的应用。
8.根据权利要求7所述的应用，其特征在于，在拱桥的外表面，利用胶粘剂将权利要求4所述的柔性加固复合材料与拱桥牢固的粘合在一起，胶粘剂的厚度为2mm；所述柔性加固复合材料包括聚脲层和预处理的机织物，其中，聚脲层作为迎爆面。
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