CN105399925B - 可快速固化聚氨酯基γ射线屏蔽复合材料及其制备方法 - Google Patents
可快速固化聚氨酯基γ射线屏蔽复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种可快速固化聚氨酯基γ射线屏蔽复合材料，属于辐射防护材料领域。采用双组份聚氨酯材料作为基体材料，填充具有屏蔽功能的金属及金属氧化物粉末制备而成，而所使用的金属氧化物可以进一步的促进复合材料的固化速率。本发明屏蔽复合材料具有固化时间快，对材料表面粘附性能好，对射线屏蔽性能好等优点，可以对各类含有放射性不规则物体的表面进行有效粘结覆盖，其附着力强不易脱落，具有良好的γ射线屏蔽性能，对检修或退役过程中含有的中低放射性的物体有很好的屏蔽效果，有效保证了相关操作人员的安全。本发明还公开了上述可快速固化聚氨酯基γ射线屏蔽复合材的制备方法。
Description
技术领域
本发明涉及一种射线屏蔽复合材料，具体讲是一种可快速固化聚氨酯基γ射线屏蔽复合材料及其制备方法，属于辐射防护材料领域。
背景技术
随着核电事业的快速发展，核电站的辐射安全问题也越来越得到人们的关注，特别是对于在核电站停堆检修以及核电设施退役的复杂环境下产生的核辐照安全问题，现已成为世界关注的焦点。
在核电站停堆检修过程中，由于回路管道法兰以及相关阀门部件的失效，往往会造成带有放射性γ射线水体的渗漏，为了保证相关从业人员的辐射安全，工作人员一般采用铅皮、铅绒毯近距离的对有渗漏的地方进行包裹处理，再由相关的工作人员替换零件。然而，由于现有的屏蔽材料对于复杂零部件的有效贴合度不够，并不能有效的防止放射性水体的渗漏，工作人员依然可能受到渗漏水体辐照的危险。
同样，在环境较为复杂的核设施退役的环境中，时常会遇到经过解体去污处理下来的形状不规则的含γ射线的各种废弃物，其在进一步的打包运输处理过程中仍然可能对操作人员造成的辐射危害。现有操作过程中，通常会采用具有射线屏蔽功能的毯子等对废弃物进行包裹覆盖，但是这些屏蔽材料灵活性差也不能有效贴合废弃物，依然存在辐射安全问题。因此，需要研发出一种可以快速固化并对物体表面有一定粘附力的屏蔽材料，在喷射到达物体表面后可以快速发泡固化对物体进行包覆屏蔽，保证相关操作人员的辐照安全。
发明内容
本发明所要解决的技术问题在于克服现有技术缺陷，提供一种可以粘附在放射物体表面且可以快速发泡固化对放射物体形成包覆屏蔽的聚氨酯基γ射线屏蔽材料及其制备方法。
为了解决上述技术问题，本发明提供的可快速固化聚氨酯基γ射线屏蔽复合材料，组成及重量份如下：
白料 105-109份
黑料 105-109份
屏蔽填料 300-600份
所述屏蔽填料为氧化铅、氧化铋、金属钨粉末其中一种或几种混合物。
本发明中，所述白料的组成及重量份为：100重量份多元醇、1.5-2.5重量份复合催化剂、1-2重量份蒸馏水、2-3重量份发泡剂、0.5-1.5重量份泡沫稳定剂。
本发明中，所述的多元醇为聚醚多元醇，所述聚醚多元醇为硬泡聚醚多元醇403、聚氧化丙烯多元醇N-303、硬泡聚醚多元醇4110、聚醚多元醇204其中一种或几种混合物，且羟值为250-800mgKOH/g。
本发明中，所述的复合催化剂为三亚乙基二胺、二甲氨基乙基醚、三甲基羟乙基双氨乙基醚、二丁基锡二月桂酸酯、辛酸亚锡、五甲基二亚乙基三胺、环已胺中的多种混合物。
本发明中，所述的发泡剂为二氯氟乙烷、环戊烷、五氟丙烷中的一种或几种混合物；
本发明中，所述泡沫稳定剂为二甲基硅油。
本发明中，所述黑料的组成及重量份为：0-50重量份二苯甲烷二异氰酸酯和50-109重量份的多亚甲基多苯基多异氰酸酯。
本发明中，所述屏蔽填料粒径为2-50um。
本发明还提供了上述可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，包括如下步骤：
1)、屏蔽填料的改性及干燥处理：
用乙醇将硅烷偶联剂溶解配置成醇溶液，取部分屏蔽填料加入硅烷偶联剂醇溶液中搅拌过滤后，进行真空干燥烘干，进行改性处理；将剩余的屏蔽填料直接进行真空干燥烘干处理；为了填料基体中具有较好的分散性能，改性与未改性的填料的比例在1:2-2:1之间；
2)、白料的混合：将白料在真空条件下搅拌均匀至液体无分层，其真空度<50kPa；
3)、填料的融入：将经过改性处理的屏蔽填料加入到白料中、将未改性干燥后的屏蔽填料加入黑料中，在真空度<50kPa条件下搅拌混合均匀；
4)、混合：将融入屏蔽填料的黑白料进行高速混合均匀，然后室温下发泡固化，所述高速混合转速至少为1500r/min。
10、根据权利要求9所述的可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于，所述如下步骤1)的真空干燥烘干条件为：真空度<80kPa、温度为120℃、烘干时间为1小时。
本发明的有益效果在于：(1)、本发明聚氨酯基γ射线屏蔽复合材料具有固化速率快，表面粘结性能好，机械性能优越等优点，通过室温下简单的混合即可快速反应固化，可以对各类含有放射性不规则物体的表面进行有效粘结覆盖，其附着力强不易脱落，具有良好的γ射线屏蔽性能，对检修或退役过程中含有的中低放射性的物体有很好的屏蔽效果，有效保证了相关操作人员的安全；(2)、本发明制备工艺简单，易于实现。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明。
实施例1
本实施例中可快速固化聚氨酯基γ射线屏蔽材料包括以下重量份组分：
组分A、105重量份白料：100重量份多元醇、1.5重量份复合催化剂、1重量份蒸馏水、2重量份发泡剂、0.5重量份二甲基硅油。
其中，100重量份聚醚多元醇为：5重量份硬泡聚醚403(羟值770-800mgKOH/g，粘度为35000-45000mPa·s)、25重量份的聚氧化丙烯多元醇N-303(480-510mgKOH/g，粘度为500-575mPa·s)和70重量份的聚醚多元醇204(270-290mgKOH/g，粘度为60-80mPa·s)；
1.5重量份的复合催化剂为：0.4重量份的五甲基二亚乙基三胺、0.1重量份的二甲氨基乙基醚、0.8重量份环已胺和0.2重量份的二丁基锡二月桂酸酯；
2重量份的发泡剂为：1.5重量份二氯氟乙烷和0.5重量份环戊烷。
组分B、105重量份黑料：50重量份二苯甲烷二异氰酸酯和55重量份多亚甲基多苯基多异氰酸酯。
组分C、300重量份屏蔽填料：240重量份的氧化铅，60重量份的钨粉，其中所用填料的粒径为2-50um。
其具体的制备步骤如下：
(1)、屏蔽填料的改性及干燥处理：用质量浓度为95％乙醇将0.5重量份的硅烷偶联剂溶解配置成醇溶液，搅拌至硅烷偶联剂完全溶解后，取80重量份氧化铅和20重量份钨粉加入硅烷偶联剂醇溶液中搅拌1小时，过滤后再用真空干燥箱除湿烘干，进行改性处理，其处理条件为：真空度<80kPa、温度为120℃、烘干时间为1小时；
取160重量份氧化铅和40重量份钨粉直接真空干燥处理，烘干条件为真空度<80kPa，温度为120℃，时间为1小时。
(2)白料的混合：将选取好的多元醇、复合催化剂、蒸馏水、发泡剂和二甲基硅油加入容器中，在真空搅拌机下搅拌均匀至液体无分层，混合条件为真空度<50kPa，搅拌时间为1小时。
(3)填料的融入：将经过改性处理的屏蔽填料加入到白料中，在真空度<50kPa情况下用真空搅拌机搅拌1小时混合均匀。将未改性干燥的屏蔽填料加入黑料中，在真空度<50kPa情况下用真空搅拌机搅拌1小时混合均匀。
(4)混合：将融入屏蔽填料的黑、白料在增力搅拌机下高速混合均匀，然后室温下发泡固化，混合转速1500r/min。
经检测，该聚氨酯基γ射线屏蔽材料的性能数据如下：
实施例2
本实施例中可快速固化聚氨酯基γ射线屏蔽材料包括以下重量份组分：
组分A、107重量份白料：100重量份多元醇、2重量份复合催化剂、1.5重量份蒸馏水、2.5重量份发泡剂、1重量份二甲基硅油。
其中，100重量份聚醚多元醇为：7.5重量份硬泡聚醚多元醇403(羟值770-800mgKOH/g，粘度为35000-45000mPa·s)、10重量份的硬泡聚醚多元醇4110(430-450mgKOH/g，粘度为2500-3000mPa·s)、10重量份的聚氧化丙烯多元醇N-303(480-510mgKOH/g，粘度为500-575mPa·s)和72.5重量份的聚醚多元醇204(270-290mgKOH/g，粘度为60-80mPa·s)；
2重量份的复合催化剂为：0.5重量份的五甲基二亚乙基三胺、0.2重量份的三甲基羟乙基双氨乙基醚，1重量份环已胺和0.35重量份的辛酸亚锡；
2.5重量份的发泡剂为：1.8重量份二氯氟乙烷和0.7重量份五氟丙烷。
组分B、107重量份黑料：107重量份多亚甲基多苯基多异氰酸酯；
组分C、400重量份的屏蔽填料：320重量份的氧化铋和80重量份的钨粉，其中所用填料粒径为2-50um。
具体的实验室成型方法步骤如下：
(1)、屏蔽填料的改性及干燥处理：用质量浓度为95％乙醇将1重量份的硅烷偶联剂溶解配置成醇溶液，搅拌至硅烷偶联剂完全溶解后，取160重量份氧化铋和40重量份钨粉加入硅烷偶联剂醇溶液中搅拌1.5小时，过滤后再用真空干燥箱除湿烘干，进行改性处理，其处理条件为：真空度<80kPa、温度为120℃、烘干时间为1小时；
取160重量份氧化铋和40重量份钨粉直接真空干燥处理，烘干条件为真空度<80kPa，温度为120℃，时间为1小时。
(2)、白料的混合：将选取好的多元醇、复合催化剂、蒸馏水、发泡剂和二甲基硅油加入容器中，在真空搅拌机下搅拌均匀至液体无分层，混合条件为真空度<50kPa，搅拌时间为1小时。
(3)、填料的融入：将经过改性处理的屏蔽填料加入到白料中，在真空度<50kPa情况下用真空搅拌机搅拌1小时混合均匀；将未改性干燥的屏蔽填料加入黑料中，在真空度<50kPa情况下用真空搅拌机搅拌1小时混合均匀。
(4)、混合：将融入屏蔽填料的黑、白料在增力搅拌机下高速混合均匀，然后室温下发泡固化，混合转速1750r/min。
经检测，该聚氨酯基γ射线屏蔽材料的性能数据如下：
实施例：3
本实施例中可快速固化聚氨酯基γ射线屏蔽材料包括以下重量份组分：
组分A、109重量份白料:100重量份多元醇、2.5重量份复合催化剂、2重量份蒸馏水、3重量份发泡剂、1.5重量份二甲基硅油。
其中，100重量份聚醚多元醇为：10重量份硬泡聚醚403(羟值770-800mgKOH/g，粘度为35000-45000mPa·s)、15重量份的硬泡聚醚多元醇4110(430-450mgKOH/g，粘度为2500-3000mPa·s)和75重量份的聚醚多元醇204(270-290mgKOH/g，粘度为60-80mPa·s)；
2.5重量份的复合催化剂为：0.6重量份的五甲基二亚乙基三胺、0.2重量份的二甲氨基乙基醚、1.4重量份环已胺和0.3重量份的三亚乙基二胺；
3重量份的发泡剂为：2.2重量份二氯氟乙烷、0.4重量份环戊烷、0.4重量份五氟丙烷。
组分B、109重量份黑料：25重量份二苯甲烷二异氰酸酯和84重量份多亚甲基多苯基多异氰酸酯。
组分C、600重量份的屏蔽填料为：240重量份的氧化铋，240重量份氧化铅，120重量份的钨粉，其中所用填料粒径为2-50um。
具体的实验室成型方法步骤如下：
(1)、屏蔽填料的改性及干燥处理：用质量浓度为95％乙醇将1.5重量份的硅烷偶联剂溶解配置成醇溶液，搅拌至硅烷偶联剂完全溶解后，取160重量份氧化铅、160重量份氧化铋和80重量份钨粉加入硅烷偶联剂醇溶液中搅拌2小时，过滤后再用真空干燥箱除湿烘干，进行改性处理，其处理条件为：真空度<80kPa、温度为120℃、烘干时间为1小时；
取80重量份氧化铅、80重量份氧化铋和40重量份钨粉直接真空干燥处理，烘干条件为真空度<80kPa，温度为120℃，时间为1小时。
(2)、白料的混合：将选取好的多元醇、复合催化剂、蒸馏水、发泡剂和二甲基硅油加入容器中，在真空搅拌机下搅拌均匀至液体无分层，混合条件为真空度<50kPa，搅拌时间为1小时。
(3)、填料的融入：将经过改性处理的屏蔽填料加入到白料中，在真空度<50kPa情况下用真空搅拌机搅拌1小时混合均匀；将未改性干燥的屏蔽填料加入黑料中，在真空度<50kPa情况下用真空搅拌机搅拌1小时混合均匀。
(4)、混合：将融入屏蔽填料的黑、白料在增力搅拌机下高速混合均匀，然后室温下发泡固化，混合转速2000r/min。
经检测，该聚氨酯基γ射线屏蔽材料的性能数据如下：
上述实施方式仅为本发明的优选实施方式，不能以此来限定本发明保护的范围，本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
Claims (8)
1.一种可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于：所述可快速固化聚氨酯基γ射线屏蔽复合材料，组成及重量份如下：
白料 105-109份
黑料 105-109份
屏蔽填料 300-600份
所述屏蔽填料为氧化铅、氧化铋、金属钨粉末其中一种或几种混合物；
所述白料的组成及重量份为：100重量份多元醇、1.5-2.5重量份复合催化剂、1-2重量份蒸馏水、2-3重量份发泡剂、0.5-1.5重量份泡沫稳定剂；
包括如下制备步骤：
1)、屏蔽填料的改性及干燥处理：
用乙醇将硅烷偶联剂溶解配置成醇溶液，取一部分屏蔽填料加入硅烷偶联剂醇溶液中搅拌过滤后，进行真空干燥烘干，进行改性处理；将剩余的屏蔽填料直接进行真空干燥烘干处理；其中，改性与未改性的填料比例在1:2-2:1之间；
2)、白料的混合：将白料在真空条件下搅拌均匀至液体无分层，其真空度<50kPa；
3)、填料的融入：将经过改性处理的屏蔽填料加入到白料中、将未改性干燥后的屏蔽填料加入黑料中，在真空度<50kPa条件下搅拌混合均匀；
4)、混合：将融入屏蔽填料的黑白料进行高速混合均匀，然后室温下发泡固化，所述高速混合转速至少为1500r/min。
2.根据权利要求1所述的可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于：所述的多元醇为聚醚多元醇，所述聚醚多元醇为硬泡聚醚多元醇403、聚氧化丙烯多元醇N-303、硬泡聚醚多元醇4110、聚醚多元醇204其中一种或几种混合物，且羟值为250-800mgKOH/g。
3.根据权利要求1所述的可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于：所述的复合催化剂为三亚乙基二胺、二甲氨基乙基醚、三甲基羟乙基双氨乙基醚、二丁基锡二月桂酸酯、辛酸亚锡、五甲基二亚乙基三胺、环己胺中的多种混合物。
4.根据权利要求1所述的可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于：所述的发泡剂为二氯氟乙烷、环戊烷、五氟丙烷中的一种或几种混合物。
5.根据权利要求1所述的可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于：所述泡沫稳定剂为二甲基硅油。
6.根据权利要求1所述的可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于：所述黑料的组成及重量份为：0-50重量份二苯甲烷二异氰酸酯和50-109重量份的多亚甲基多苯基多异氰酸酯。
7.根据权利要求1所述的可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于：所述屏蔽填料粒径为2-50um。
8.根据权利要求1所述的可快速固化聚氨酯基γ射线屏蔽复合材料的制备方法，其特征在于，所述如下步骤1)的真空干燥烘干条件为：真空度<80kPa、温度为120℃、烘干时间为1小时。
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| CN112063159B (zh) * | 2020-09-07 | 2022-09-16 | 圣华盾防护科技股份有限公司 | 一种透气式X/γ射线屏蔽复合材料及其制备方法 |
| CN116082826B (zh) * | 2023-02-02 | 2024-02-09 | 北京航空材料研究院股份有限公司 | 一种防辐射聚氨酯弹性体、胶片和复合玻璃及其制备方法 |
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