CN113235295B - 混合金属化防核辐射材料及其制备方法和服装 - Google Patents

混合金属化防核辐射材料及其制备方法和服装 Download PDF

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CN113235295B
CN113235295B CN202110485647.8A CN202110485647A CN113235295B CN 113235295 B CN113235295 B CN 113235295B CN 202110485647 A CN202110485647 A CN 202110485647A CN 113235295 B CN113235295 B CN 113235295B
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CN113235295A (zh
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卜庆革
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Qingdao Hengtong X Silver Specialty Textile Co ltd
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Abstract

本发明公开混合金属化防核辐射材料及其制备方法和服装。本发明的方法能够在非金属材料的表面形成打底铜层，大大增强功能金属金或铂金与非金属材料表面的结合力。由此得到能够满足制作服装特别是防护服要求的功能材料。本发明的方法得到的功能材料具有优异的耐高温性、柔韧性、耐弯折、轻量化等特性，而且具有金属特别是金和铂金的特性，不仅具有很好的导电性，而且还具有优选的磁屏蔽性能，并能够对x‑射线、r‑射线等具有防护效果，防护效果在同等状态下是铅橡胶的10～15倍，而重量仅为铅橡胶衣的十分之一至四十五分之一。本发明的材料可广泛应用于国防、军事、医疗、民用等方面。

Description

混合金属化防核辐射材料及其制备方法和服装
技术领域
本发明涉及混合金属化材料，具体地涉及具有射线防护功能的混合金属化材料及其制备方法和由此得到的服装，特别是防护服。
背景技术
在电子、医疗精密仪器和生化防护等领域存在对于抗静电、抗电磁干扰和防护射线材料的需求。随着工业和科学技术的进步，对材料性能的需求越来越广泛，也越来越高。非金属材料，特别是织物纤维等因其优异的加工性、轻量化具有巨大应用前景，然而抗静电、抗电磁干扰或射线防护性能是金属材料，甚至是特定金属的性能，并不是织物等非金属材料本身的性能。因此这些非金属材料不能直接应用于这些领域。非金属材料的功能化是解决方案之一。
在非金属材料的金属化方面，目前的方法一般均涉及非金属材料的处理步骤。例如，CN 105484043 A公开了一种以金属化合物为导电成分制备涤纶导电纤维的方法，该方法包括将涤纶纤维进行除油，并在碱性溶液中进行粗化处理；采用一定浓度的苯胺溶液在一定酸度和氧化剂存在下对涤纶纤维表面进行嫁接聚合；以铜盐为氧化剂，亚硫酸钠或硫代硫酸钠为还原剂采用氧化还原反应法在处理过的纤维上形成铜的硫化物导电镀层。该方法涉及对非金属材料涤纶纤维的表面进行嫁接聚合的步骤。
再例如，CN106702356A公开了一种导电聚酰亚胺纤维制备方法，其包括预处理及洗涤、表面改性、负载Pd、化学镀金属步骤，在避免采用有毒、有害化学物质进行粗化处理的情况下实现导电聚酰亚胺纤维的制备。其中涉及使用含有巯基和氨基的化合物溶液对聚酰亚胺纤维进行表面改性的步骤。
虽然上述现有技术均得到了具有良好导电性能的柔性纤维材料，但是这些材料的功能仍然有限，特别是不具有射线防护功能。
背景技术中的信息仅仅在于说明本发明的总体背景，不应视为承认或以任何形式暗示这些信息构成本领域一般技术人员所公知的现有技术。
发明内容
为解决现有技术中的至少部分技术问题，本发明提供一种混合金属化材料，其具有优异的金属特性，特别是金和铂金的特性。至少部分地基于此完成了本发明。具体地，本发明包括以下内容。
本发明的一方面，提供一种混合金属化材料的制备方法，其包括以下步骤：
(1)用氯化锌的盐酸预处理液浸泡原材料1-30分钟，加DMF清洗，甩干后于例如110-130℃烘干得到预处理材料；
(2)用处理液处理所述预处理材料从而使其导电率为每厘米40-50欧姆，由此得到处理材料，其中所述处理液包含焦磷酸铜、硫酸铜、焦磷酸钾、氨水、氯化钯和甲酸；和
(3)在所述处理材料表面电镀金，然后通过化学镀铂金，以使原材料重量增加2-3倍，由此得到混合金属化材料。
根据本发明所述的混合金属化材料的制备方法，优选地，所述原材料为选自涤纶纤维、锦纶纤维、聚酰亚胺纤维、芳纶纤维、PBO纤维、玻璃纤维、碳纤维组成的组中的至少一种纤维。
根据本发明所述的混合金属化材料的制备方法，优选地，所述原材料为选自涤纶纤维、锦纶纤维、聚酰亚胺纤维、芳纶纤维、PBO纤维、玻璃纤维、碳纤维组成的组中的至少一种纤维制备的布料。
根据本发明所述的混合金属化材料的制备方法，优选地，所述预处理液包含4.5-5.5g/L的氯化锌和0.8-1.21g/L盐酸。
根据本发明所述的混合金属化材料的制备方法，优选地，所述处理液中焦磷酸铜的浓度为6.5-7.5g/L，硫酸铜的浓度为4.5-5.5g/L，焦磷酸钾的浓度为1.5-2.5g/L，氨水的浓度为4.5-5.5g/L，氯化钯的浓度为0.8-1.2g/L，甲酸的浓度为9-12g/L。
根据本发明所述的混合金属化材料的制备方法，优选地，所述混合金属化纤维中金与铂金的重量比为(6.5-7.5):(3.5-3.5)。
本发明的第二方面，提供一种混合金属化材料，其通过本发明第一方面所述的方法制备得到。
本发明的第三方面，提供一种服装，其包含本发明第二方面所述的混合金属化材料或由其制作得到。优选地，服装为用于防护射线辐射的防护服，所述射线包括x-射线和/或γ-射线。
本发明的方法能够通过一步反应在非金属材料的表面形成铜层，然后以该铜层打底，大大增强金或铂金与非金属材料表面的结合力。由此得到能够满足制作服装特别是防护服要求的功能材料。本发明的方法得到的功能材料具有优异的耐高温性、柔韧性、耐弯折、轻量化等特性，而且具有金属特别是金和铂金的特性。已知金和铂金对于射线的防护远大于对传统铅的防护，因此本发明的材料不仅具有很好的导电性，而且还具有优选的磁屏蔽性能，并能够对x-射线、r-射线等具有防护效果，防护效果在同等状态下是铅橡胶的10～15倍，而重量仅为铅橡胶衣的十分之一至四十五分之一。本发明的材料可广泛应用于国防、军事、医疗、民用等方面。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为具体公开了该范围的上限和下限以及它们之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。除非另有说明，否则“％”为基于重量的百分数。
本发明的混合金属化材料是指在非金属材料上镀覆金属表层从而使非金属材料具备金属特性的材料。本发明中，非金属材料一般是指具有良好加工性，能够用于制作衣物的柔性材料，其实例包括但不限于织物，如涤纶纤维、锦纶纤维、聚酰亚胺纤维、芳纶纤维、PBO纤维，以及其他可制作特殊用途衣物的非金属纤维材料，如玻璃纤维、碳纤维等。本发明的方法中可以使用上述材料中的一种或多种的组合。
本发明的非金属材料优选进一步进行改性处理，从而增强其与金属的结合。示例性改性方法包括在材料表面引入活性基团的方法。活性基因的实例包括巯基、氨基或-CN等。
本发明的混合金属化材料制备方法一般包括以下步骤：
(1)用氯化锌的盐酸预处理液浸泡原材料1-30分钟，加DMF清洗，甩干后于110-130℃烘干得到预处理材料；
(2)用处理液处理所述预处理材料从而使其导电率为每厘米40-50欧姆，由此得到处理材料，其中所述处理液包含焦磷酸铜、硫酸铜、焦磷酸钾、氨水、氯化钯和甲酸；和
(3)在所述处理材料表面电镀金，然后通过化学镀铂金，以使原材料重量增加2-3倍，由此得到混合金属化材料。
本发明的制备方法中，预处理液包含氯化锌和盐酸。其中氯化锌的含量一般为4-6g/L，优选4.5-5.5g/L，更优选4.5-5g/L。盐酸的用量控制为使HCl在预处理液中的浓度为0.5-2g/L，优选0.8-1.5g/L，更优选1.0-1.2g/L。预处理液能够有效除去材料表面的杂质。预处理后使用清洗液进行洗涤。清洗液的实例包括DMF等。预处理的材料需要进一步进行烘干处理，烘干温度根据材料性质而设置，一般为110-125℃。
本发明的制备方法中，处理液用于对材料进行打底，增强非金属材料与金和铂金之间的结合力。处理液包含焦磷酸铜、硫酸铜、焦磷酸钾、氨水、氯化钯和甲酸。本发明发现通过使用处理液能够在不使用敏化液的情况下使钯还原并结合到纤维表面，并在表面形成活化中心，引发化学镀反应，最终在表面形成具有强结合力的铜层。
需要说明的是，本发明的步骤2用于形成打底层，因此需要严格控制反应，避免形成较厚的铜层而影响材料性能，特别是防护性能。为此可控制反应当材料的导电率达到每厘米30-50欧姆时终止反应即可。导电率越低，说明表面形成的铜越多，影响材料性能。另一方面，导电率越高，说明表面形成的铜越少，不利于金或铂金的结合。
根据本发明所述的混合金属化材料的制备方法，处理液中焦磷酸铜的浓度一般为6.5-7.5g/L，优选6.7-7.2g/L，更优选6.8-7.1g/L。硫酸铜在处理液中的浓度一般为4.5-5.5g/L，优选4.6-5.3g/L，更优选4.8-5.2g/L。焦磷酸钾的浓度一般为1.5-2.5g/L，优选1.6-2.4g/L，更优选1.8-2.0g/L。氨水的浓度一般为4.5-5.5g/L，优选4.6-5.3g/L，更优选4.8-5.0g/L。氯化钯的浓度一般为0.8-1.2g/L，优选为0.9-1.1g/L。甲酸的浓度一般为9-12g/L，优选9.5-11g/L，更优选10-11g/L。
根据本发明所述的混合金属化材料的制备方法，混合金属化纤维中，作为功能层是金与铂金的混合层，其中功能层中金与铂金的重量比一般控制为(6.5-7.5):(3.5-3.5)，优选7:3。混合层中金与铂金的量可通过本领域已知的方法进行控制。一般而言，可通过控制反应进行的时间、反应液的组成等而容易地实现。
本发明的混合金属化材料的形式不特别限定，包括纤维材料形式，面料或布料材料形式。在面料或布料的情况下，其制备方法可以是由混合金属化纤维材料制备得到的面料或布料，也可以是将面料或布料作为原料进行本发明的制备方法而直接得到混合金属化材料。
本发明面料或布料因其优异的功能，例如辐射屏蔽性和防护性能可用于进一步制作服装，特别是功能性服装或工服，如防护射线辐射的防护服。由于金和铂金本身性质可知，本发明的防护服能够有效的防护包括x-射线和/或γ-射线在内有射线。另外，本发明得到的面料或布料中混合金属的结合力强，可经受正常情况下50次以上的洗涤而不会发现明显的金属脱落。
实施例1
本实施例为一种混合金属化金、铂金纤维材料的制备例，其中使用涤纶纤维布料作为示例性原材料。具体包括以下步骤：
①用氯化锌5g/L+盐酸1g/L，浸泡5分钟再清洗干净，再加DMF清洗2分钟，甩干。在120℃±5℃的烘箱内烘30分钟。
②用焦磷酸铜7g/L+硫酸铜5g/L+焦磷酸钾2g/L+氨水5g/L+氯化钯1g/L+甲酸10g/L沉积铜导体，致导电率为每厘米50欧姆时终止反应得到处理材料。
③在步骤②的处理材料的表面以1.2A/dm的电流密度进行电镀，时间为5分钟。
④以步骤③得到的材料为基体进一步进行化学镀铂金，控制步骤③和④使镀覆的金与铂金的重量比为7:3。
取500g本实施例得到的布料放5g无磷洗衣粉，用型号为Electrolux的全自动滚筒欧式洗衣机机洗，脱水转速650r/min，护理程序选择冷水超快洗涤。洗衣机从启动到自动停止记为洗涤1次，对本实施例的布料洗涤50次屏蔽性能不下降。
实施例2
本实施例为一种混合金属化金、铂金纤维材料的制备例，其中使用玻璃纤维作为示例性原材料。具体包括以下步骤：
①用氯化锌4.5g/L+盐酸1g/L，浸泡5分钟再清洗干净，再加DMF清洗2分钟，甩干。在120℃±5℃的烘箱内烘30分钟。
②用焦磷酸铜7.3g/L+硫酸铜5.5g/L+焦磷酸钾2.5g/L+氨水5.5g/L+氯化钯1.3g/L+甲酸10g/L沉积铜导体，致导电率为每厘米40欧姆时终止反应得到处理材料。
③在步骤②的处理材料的表面以1.5A/dm的电流密度进行电镀，时间为3分钟。
④以步骤③得到的材料为基体进一步进行化学镀铂金，控制步骤③和④使镀覆的金与铂金的重量比为7.5:2.5。
取500g本实施例得到的布料放5g无磷洗衣粉，用型号为Electrolux的全自动滚筒欧式洗衣机机洗，脱水转速650r/min，护理程序选择冷水超快洗涤。洗衣机从启动到自动停止记为洗涤1次，对本实施例的纤维制作的布料洗涤50次屏蔽性能不下降。
实施例3
本实施例为一种混合金属化金、铂金纤维材料的制备例，其中使用浸泡到0.1M/L半胱胺盐酸盐溶液中在50℃浸泡40分钟得到改性聚酰亚胺纤维布料作为示例性原材料。具体包括以下步骤：
①用氯化锌5g/L+盐酸1g/L，浸泡5分钟再清洗干净，再加DMF清洗2分钟，甩干。在120℃±5℃的烘箱内烘30分钟。
②用焦磷酸铜7g/L+硫酸铜5g/L+焦磷酸钾2g/L+氨水5g/L+氯化钯1g/L+甲酸10g/L沉积铜导体，致导电率为每厘米50欧姆时终止反应得到处理材料。
③在步骤②的处理材料的表面以1.2A/dm的电流密度进行电镀，时间为5分钟。
④以步骤③得到的材料为基体进一步进行化学镀铂金，控制步骤③和④使镀覆的金与铂金的重量比为7:3。
取500g本实施例得到的布料放5g无磷洗衣粉，用型号为Electrolux的全自动滚筒欧式洗衣机机洗，脱水转速650r/min，护理程序选择冷水超快洗涤。洗衣机从启动到自动停止记为洗涤1次，对本实施例的布料洗涤63次屏蔽性能不下降。
比较例1
本比较例为一种混合金属化金、铂金纤维材料的制备例，其中使用涤纶纤维布料作为示例性原材料。具体包括以下步骤：
①用氯化锌5g/L+盐酸1g/L，浸泡5分钟再清洗干净，再加DMF清洗2分钟，甩干。在120℃±5℃的烘箱内烘30分钟。
②用焦磷酸铜7g/L+硫酸铜5g/L+焦磷酸钾2g/L+氨水5g/L沉积铜导体，得到处理材料。
③在步骤②的处理材料的表面以1.5A/dm的电流密度进行电镀，时间为3分钟。
④以步骤③得到的材料为基体进一步进行化学镀铂金，控制步骤③和④使镀覆的金与铂金的重量比为7.5:2.5。
取500g本实施例得到的布料放5g无磷洗衣粉，用型号为Electrolux的全自动滚筒欧式洗衣机机洗，脱水转速650r/min，护理程序选择冷水超快洗涤。洗衣机从启动到自动停止记为洗涤1次，对本比较例的布料洗涤32次屏蔽性能不下降。
比较例2
本比较例为一种混合金属化金、铂金纤维材料的制备例，其中使用涤纶纤维布料作为示例性原材料。具体包括以下步骤：
①用氯化锌5g/L+盐酸1g/L，浸泡5分钟再清洗干净，再加DMF清洗2分钟，甩干。在120℃±5℃的烘箱内烘30分钟。
③在步骤①的处理材料的表面以1.5A/dm的电流密度进行电镀，时间为3分钟。
③对步骤②得到的材料为基体进一步进行化学镀铂金，控制步骤②和③使镀覆的金与铂金的重量比为7.5:2.5。
取500g本实施例得到的布料放5g无磷洗衣粉，用型号为Electrolux的全自动滚筒欧式洗衣机机洗，脱水转速650r/min，护理程序选择冷水超快洗涤。洗衣机从启动到自动停止记为洗涤1次，对本比较例的布料洗涤21次屏蔽性能不下降。
尽管本发明已经参考示例性实施方案进行了描述，但应理解本发明不限于公开的示例性实施方案。在不背离本发明的范围或精神的情况下，可对本发明说明书的示例性实施方案做多种调整或变化。权利要求的范围应基于最宽的解释以涵盖所有修改和等同结构与功能。

Claims (3)

1.一种混合金属化材料的制备方法，其特征在于，包括以下步骤：
(1)用氯化锌的盐酸预处理液浸泡原材料1-30分钟，加DMF清洗，甩干后烘干得到预处理材料；
(2)用处理液处理所述预处理材料从而使其导电率为每厘米40-50欧姆，由此得到处理材料，其中所述处理液包含6.5-7.5g/L焦磷酸铜、4.5-5.5g/L硫酸铜、1.5-2.5g/L焦磷酸钾、4.5-5.5g/L氨水、0.8-1.2g/L氯化钯和9-12g/L甲酸；和
(3)在所述处理材料表面电镀金，然后通过化学镀铂金，以使原材料重量增加2-3倍，由此得到混合金属化材料；
所述原材料为选自聚酰亚胺纤维、芳纶纤维、PBO纤维、玻璃纤维、碳纤维组成的组中的至少一种纤维或由其制备的布料。
2.根据权利要求1所述的混合金属化材料的制备方法，其特征在于，所述预处理液包含4.5-5.5g/L的氯化锌和0.8-1.21g/L盐酸。
3.根据权利要求1所述的混合金属化材料的制备方法，其特征在于，所述混合金属化纤维中金与铂金的重量比为(6.5-7.5):(3.5-3.5)。
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