CN112552600B - 滚塑用中子屏蔽材料及具有中子屏蔽效果的滚塑制品 - Google Patents
滚塑用中子屏蔽材料及具有中子屏蔽效果的滚塑制品 Download PDFInfo
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- 230000000694 effects Effects 0.000 title claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 38
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- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
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- 229940049676 bismuth hydroxide Drugs 0.000 claims description 2
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
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- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
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- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种滚塑用中子屏蔽材料及具有中子屏蔽效果的滚塑制品，本发明的滚塑用中子屏蔽材料，包括A料和B料，其中，A料包括如下重量份的组分：聚丙烯100份、第一抗氧剂0.2‑1份、第一润滑剂0.1‑0.5份、重金属化合物10‑25份、含硼元素纤维10‑30份；B料包括：聚丙烯100份、第二抗氧剂0.2‑1份、第二润滑剂0.1‑0.5份、含硼元素的化合物5‑20份；含硼元素的化合物为非纤维状材料。本发明的滚塑用中子屏蔽材料制备过程简单，材料耐热性能好，具有较高的辐射屏蔽效率，所成型的具有中子屏蔽效果的滚塑制品结构可设计，满足不同设施的辐射屏蔽需求，能有效减少中子对人员和环境造成的影响。
Description
技术领域
本发明涉及中子屏蔽技术领域，尤其涉及一种滚塑用中子屏蔽材料及具有中子屏蔽效果的滚塑制品。
背景技术
滚塑成型又称旋转模塑或回转成型，是将事先配比好的一定量的塑料粉末加入模具，模具随机器的转臂做空间球面运动并进行加热，塑料粉末在重力和热传导、热辐射的作用下逐渐熔化并贴覆于模具的成型表面，然后经过冷却，脱模得到制品。滚塑工艺能够成型表面积大、厚度均匀，内外表面平滑的中空塑料制品，如大型储罐、容器、游艇等。
随着核能、辐照加工、无损检测、放射医疗等产业的快速发展，高能射线已广泛应用于工业、医疗、科研等多个领域。常见的高能射线包括X射线、γ射线和中子等，高能射线的辐射与防护问题一直是人们关注的重点。中子产生的辐射危害有效性约通常是射线的2.5倍，中子的屏蔽比单纯的γ射线屏蔽也要复杂得多，既要考虑快中子、热中子的屏蔽，还要考虑屏蔽材料与中子发生作用而发出γ射线的情况，所以在实际工作中对中子的屏蔽防护变得更为复杂。中子屏蔽材料在国防科研、放射性医学、核工业和航空航天等领域具有广泛的应用，它能够防止中子射线进入人体活动空间，保护人员的安全。
传统的中子屏蔽材料主要以硼基或铅基聚乙烯复合屏蔽材料为主体。这类材料对快中子的减速和慢中子的捕获具有良好的效果，自上世纪80年代研制成功以来，得到了广泛的应用。硼基或铅基聚乙烯复合屏蔽材料虽然具有屏蔽中子与射线的综合效果，但由于耐热性较差且强度低，不适宜应用于有温度要求的工作环境，致其寿命极短，使用更换频繁。传统的中子屏蔽材料采用聚合物和铅、硼等填料直接共混的方式制备，所得到中子屏蔽材料屏蔽效率较低，需要较高的填料添加量和较大的厚度才能达到较好的屏蔽效率。
此外，核实验与应用过程中的设备外形各异，结构复杂。目前常用的中子屏蔽材料多为板材或片材结构，难以加工成大尺寸，外形复杂的屏蔽防护装置，因而在实际应用中受到较多限制，使用效果不理想。
发明内容
为解决上述技术问题，本发明的目的是提供一种滚塑用中子屏蔽材料及具有中子屏蔽效果的滚塑制品，本发明的滚塑用中子屏蔽材料制备过程简单，材料耐热性能好，具有较高的辐射屏蔽效率，所成型的具有中子屏蔽效果的滚塑制品结构可设计，满足不同设施的辐射屏蔽需求，能有效减少中子对人员和环境造成的影响。
本发明的第一个目的是提供一种滚塑用中子屏蔽材料，包括A料和B料，其中：
A料包括如下重量份的组分：
聚丙烯100份、第一抗氧剂0.2-1份、第一润滑剂0.1-0.5份、重金属化合物10-25份、含硼元素纤维10-30份；
B料包括如下重量份的组分：
聚丙烯100份、第二抗氧剂0.2-1份、第二润滑剂0.1-0.5份、含硼元素的化合物5-20份；含硼元素的化合物为非纤维状材料。
进一步地，A料与B料的质量比为1:2-2:1。
进一步地，A料与B料中的聚丙烯的简支梁缺口冲击强度≥20KJ/m2，230℃及2.16kg条件下的熔融指数为10-50g/10min。
进一步地，重金属化合物为氧化钨、碳酸钡、硫酸钡、醋酸铅、氧化铅、辛酸铅、氧化铋和氢氧化铋中的一种或几种，重金属化合物的粒径为200-1000目，纯度为99％以上。
进一步地，含硼元素纤维为硼纤维和/或氮化硼纤维，含硼元素纤维长度为3-10mm。
进一步地，含硼元素的化合物为氧化硼、硼酸、氮化硼和碳化硼中的一种或几种，粒径为200-1000目，纯度为99％以上。
进一步地，第一抗氧剂和第二抗氧剂分别独立地选自抗氧剂1010、抗氧剂168、抗氧剂1076、抗氧剂445、抗氧剂245、抗氧剂3114、抗氧剂1035、抗氧剂1098、抗氧剂1024、抗氧剂300、抗氧剂618、抗氧剂626、抗氧剂DSTDP、抗氧剂DLTDP、抗氧剂RD、抗氧剂MBZ和抗氧剂330中的一种或几种。优选地，第一抗氧剂和第二抗氧剂分别独立地选自抗氧剂1010、抗氧剂168和抗氧剂1076中的一种或几种。
进一步地，第一润滑剂和第二润滑剂分别独立地选自硬脂酸锌、硬脂酸钙、乙撑双硬脂酰胺、硬脂酸酰胺、硬脂酸甘油酯、芥酸酰胺、油酸酰胺、硅酮、聚乙烯蜡和聚丙烯蜡中的一种或几种。优选地，第一润滑剂和第二润滑剂分别独立地选自硬脂酸钙、硬脂酸锌、乙撑双硬脂酰胺和芥酸酰胺中的一种或几种。
进一步地，A料与B料还包括添加剂，A料与B料中的添加剂分别独立地选自光稳定剂、偶联剂、抗静电剂、成核剂、阻燃剂、色粉和加工助剂中的一种或几种。
润滑剂、光稳定剂、成核剂、阻燃剂、色粉和加工助剂的含量没有具体限定，均可以为本领域技术人员所熟知的常规含量，或可以根据实际情况的要求来进行适当调整。
本发明的第二个目的是公开一种具有中子屏蔽效果的滚塑制品的制备方法，采用本发明的上述滚塑用中子屏蔽材料制备，包括以下步骤：
（1）将聚丙烯、第一抗氧剂、第一润滑剂和重金属化合物熔融共混后造粒磨粉，然后将磨好的粉料与含硼元素纤维混匀后得到A料；
将聚丙烯、第二抗氧剂、第二润滑剂和含硼元素的化合物熔融共混后造粒磨粉，得到B料；
（2）将A料先进行滚塑成型，A料中的组分依次形成由外到内的γ射线吸收层和中子吸收层；待A料熔融成型后，再加入B料进行滚塑成型，B料在所述中子吸收层的内侧成型为中子慢化层。
进一步地，在步骤（1）中，熔融共混可用单螺杆挤出机、双螺杆挤出机或密炼机，熔融共混加工温度为190-230℃。磨粉可用塑料磨粉机，工艺参数为磨粉电流60-90A，磨盘转速2000-4000rpm。
优选地，步骤（1）如下：
先按重量配备好各原料，将聚丙烯、第一抗氧剂、第一润滑剂和重金属化合物在高速混合机中以50rpm的速度搅拌8分钟得到混合物1；将混合物1熔融共混后，造粒磨粉；将磨好的粉料与含硼元素纤维在高速混合机中以30rpm的速度搅拌3分钟得到A料；
先按重量配备好各原料，将聚丙烯、第二抗氧剂、第二润滑剂和含硼元素的化合物在高速混合机中以50rpm的速度搅拌8分钟得到混合物2；将混合物2熔融共混后，造粒磨粉得到B料。
本发明的滚塑用中子屏蔽材料在滚塑成型过程中，A料中的聚丙烯粉末首先熔融粘附于模具内表面，A料中的含硼元素纤维长度较大，会聚集在A料内层，而重金属化合物聚集在最外层的聚丙烯中。待A料完全熔融后，加入B料。成型的滚塑制品具有多层结构，包括A料形成的外层和中间层，以及B料形成的内层，其中最内层的聚丙烯和含硼元素的化合物（来源于B料）可慢化快中子，作为中子慢化层，中间的含硼元素纤维层（来源于A料）可以吸收慢中子，作为中子吸收层，最外层中的重金属化合物（来源于A料）可以吸收次级γ射线，作为γ射线吸收层。
本发明还要求保护一种采用以上制备方法所制备的具有中子屏蔽效果的滚塑制品，包括A料形成的外层和中间层以及B料形成的内层，外层为γ射线吸收层，中间层为中子吸收层，内层为中子慢化层。
借由上述方案，本发明至少具有以下优点：
1、本发明的滚塑用中子屏蔽材料分别使用了含硼元素纤维和含硼元素的化合物，二者在成型后分布在制品的不同位置，可实现不同的中子吸收效果。含硼元素的化合物分布在制品的最内层，可以慢化快中子，含硼元素纤维分布在制品的中间层，可以吸收慢中子，最外层的重金属化合物可以吸收γ射线。本发明的中子屏蔽材料，配方设计合理，通过上述成型方法，仅需较低的填料添加量和较小的制品厚度便可得到具有较好屏蔽效率的制品。
2、本发明滚塑专用料制备方法简单，成型的制品具有多层结构，可同时实现中子慢化、吸收，并屏蔽次级γ射线，极大地提高了材料的中子屏蔽效率，满足辐射防护的综合屏蔽要求。成型的制品内外表面光滑，机械强度高、耐热性能好，使用温度范围广，中子透射率＜2%。可根据成型模具，制备出不同尺寸，外形复杂的屏蔽防护装置，满足不同场景下的使用要求。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合详细说明如后。
附图说明
图1是本发明具有中子屏蔽效果的滚塑制品的剖面结构示意图；
附图标记说明：
1-γ射线吸收层；2-中子吸收层；3-中子慢化层。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例
表1 A料和B料的配方组成
利用上述实施例中的滚塑用中子屏蔽材料制备滚塑制品，步骤如下：
（1）先按重量配备好各原料，将聚丙烯、第一抗氧剂、第一润滑剂和重金属化合物在高速混合机中以50rpm的速度搅拌8分钟得到第一混合物；将第一混合物熔融共混后，造粒磨粉；将磨好的粉料与含硼元素纤维在高速混合机中以30rpm的速度搅拌3分钟得到A料；
先按重量配备好各原料，将聚丙烯、第二抗氧剂、第二润滑剂和含硼元素的化合物在高速混合机中以50rpm的速度搅拌8分钟得到第二混合物；将第二混合物熔融共混后，造粒磨粉得到B料。熔融共混可用单螺杆挤出机、双螺杆挤出机或密炼机，熔融共混加工温度为210℃。磨粉可用塑料磨粉机，工艺参数为磨粉电流75A，磨盘转速3000rpm。
（2）将A料先进行滚塑成型，A料中的组分依次形成由外而内的γ射线吸收层1和中子吸收层2；待A料熔融成型后，再加入B料进行滚塑成型，B料形成中子慢化层3。所制备的滚塑制品的结构如图1所示。
测试以上所制备的滚塑制品的性能，测试条件如下：
弯曲性能测试：按照ISO-178标准测试；
简支梁缺口冲击强度：按照ISO-179标准测试；
负荷变形温度：按照ISO-75标准测试；
维卡软化点：按照ISO-306标准测试；
中子屏蔽性能测试：采用Am-Be中子源测试，置于石蜡箱中的中子源活度为1.11×1010Bq，源箱面到探测器的一端有深13cm、直径11cm的圆柱形开口，中子探测器为3He正比计数管，放置于距源50cm处，并且正对源箱开口。试样位于源与计数管之间，紧贴着源箱开口。紧贴中子探测器放置NaIγ谱仪探测器，测量中子屏蔽材料产生的次级γ射线。
结果如表2所示。
表2 不同材料成型制品的性能测试结果
以上仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。
Claims (9)
1.一种具有中子屏蔽效果的滚塑制品的制备方法，其特征在于，包括以下步骤：
（1）将聚丙烯、第一抗氧剂、第一润滑剂和重金属化合物熔融共混后造粒磨粉，然后将磨好的粉料与含硼元素纤维混匀后得到A料；
将聚丙烯、第二抗氧剂、第二润滑剂和含硼元素的化合物熔融共混后造粒磨粉，得到B料；
（2）将所述A料先进行滚塑成型，所述A料中的组分依次形成由外到内的γ射线吸收层和中子吸收层；待A料熔融成型后，再加入B料进行滚塑成型，所述B料在所述中子吸收层的内侧成型为中子慢化层；
其中，所述A料包括如下重量份的组分：
聚丙烯100份、第一抗氧剂0.2-1份、第一润滑剂0.1-0.5份、重金属化合物10-25份、含硼元素纤维10-30份；
所述B料包括如下重量份的组分：
聚丙烯100份、第二抗氧剂0.2-1份、第二润滑剂0.1-0.5份、含硼元素的化合物5-20份；所述含硼元素的化合物为非纤维状材料。
2.根据权利要求1所述的制备方法，其特征在于：所述A料与B料的质量比为1:2-2:1。
3.根据权利要求1所述的制备方法，其特征在于：所述A料与B料中的聚丙烯的简支梁缺口冲击强度≥20kJ/m2，230℃及2.16kg条件下的熔融指数为10-50g/10min。
4.根据权利要求1所述的制备方法，其特征在于：所述重金属化合物为氧化钨、碳酸钡、硫酸钡、醋酸铅、氧化铅、辛酸铅、氧化铋和氢氧化铋中的一种或几种，所述重金属化合物的粒径为200-1000目。
5.根据权利要求1所述的制备方法，其特征在于：所述含硼元素纤维为硼纤维和/或氮化硼纤维，所述含硼元素纤维长度为3-10mm。
6.根据权利要求1所述的制备方法，其特征在于：所述含硼元素的化合物为氧化硼、硼酸、氮化硼和碳化硼中的一种或几种，粒径为200-1000目。
7.根据权利要求1所述的制备方法，其特征在于：所述A料与B料还包括添加剂，所述A料与B料中的添加剂分别独立地选自光稳定剂、偶联剂、抗静电剂、成核剂、阻燃剂、色粉和加工助剂中的一种或几种。
8.根据权利要求1所述的制备方法，其特征在于：在步骤（1）中，所述熔融共混采用单螺杆挤出机、双螺杆挤出机或密炼机，熔融共混加工温度为190-230℃。
9.一种权利要求1-8任一项所述的制备方法所制备的具有中子屏蔽效果的滚塑制品，其特征在于，包括A料形成的外层和中间层，以及B料形成的内层，所述外层包括γ射线吸收层，中间层包括中子吸收层，内层包括中子慢化层。
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