High Temperature Resistant Epoxy Resin-Based Composites by Casting Process for Neutron Shielding

doi:10.19894/j.issn.1000-0518.230164

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (10): 1420-1429.DOI: 10.19894/j.issn.1000-0518.230164

• Full Papers • Previous Articles Next Articles

High Temperature Resistant Epoxy Resin-Based Composites by Casting Process for Neutron Shielding

Zhi-Peng HAN¹, Chong QIN², Jin-Xiang ZHOU², Ming YU³, Zhao-Bin CHEN²()

^1.Marine Equipment Shenyang Bureau，Changchun 130033，China
^2.Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Polymer Composites Engineering Laboratory，Changchun 130022，China
^3.Second Institute of Ship Design and Research of Wuhan，Wuhan 430205，China

Received:2023-06-05 Accepted:2023-08-22 Published:2023-10-01 Online:2023-10-13
Contact: Zhao-Bin CHEN
About author:zhaobinchen@ciac.ac.cn

Abstract

Abstract:

Based on the proposed concept of “self-driven gradient temperature rising”， the epoxy resin-based composites with high temperature resistance for neutron shielding are developed， which is realized by casting and curing at room temperature. The matrix of the composite is determined by the reaction kinetics study as a mixture of mixed multifunctional glycidylamine epoxy resins and mixed modified phenolic amine curing agents. Through comprehensive studies on the matching between rigid and flexible groups in the molecular structure of resins and curing agents， heat transfer in complex phases， and screening of functional fillers， the composites for neutron shielding with excellent physical and mechanical properties are obtained， of which the glass transition temperature （T_g） is higher than 150 ℃， the load heat deformation temperature is higher than 150 ℃， the fast neutron shielding coefficient （²⁵²Cf， 40 mm） is higher than 2.5， and the thermal neutron shielding rate （²⁵²Cf， 40 mm） is higher than 99.9%. This kind of high temperature resistant epoxy resin-based composites shows great potentials in the field of secondary shielding of nuclear radiation under harsh service conditions in real applications.

Key words: Room temperature casting, Epoxy resin, Phenolic amine curing agent, High temperature resistance, Neutron shielding

CLC Number:

O615.5

Zhi-Peng HAN, Chong QIN, Jin-Xiang ZHOU, Ming YU, Zhao-Bin CHEN. High Temperature Resistant Epoxy Resin-Based Composites by Casting Process for Neutron Shielding[J]. Chinese Journal of Applied Chemistry, 2023, 40(10): 1420-1429.

Figures/Tables 12

Fig.1 Schematic diagram for neutron shielding simulation

Fig.2 Typical molecular structure of main epoxy resins and curing agents

Fig.3 DSC images of curing process of different epoxy resins and curing agents

Table 1 Thermodynamic parameters of solidification of resins at different heating rates by DSC analysis

Heating rate β/（K·min^－1）	Initial temperature T_i/℃	Peak temperature T_p/℃	Termination temperature T_f/℃
5	54.95	95.67	154.32
10	58.72	105.95	162.13
15	65.23	116.80	166.49
20	72.16	121.15	173.22

Fig.4 （A） SEM images of BN（a.CGF12； b.CG20； c.4F； d.QS30）；（B） Effects of different BN powders on thermal conductivity of matrix materials

Table 2 Simulation results of thermal conductivity of composite materials

Packing	Packing shape	$V f$	$λ f$ /（W·m^－1·K^－1）	$λ p$ /（W·m^－1·K^－1）	A	$V m$	$λ$ /（W·m^－1·K^－1）
B₄C	Block	0.25	10	0.227	1.5	0.637	0.432
B₄C	Block	0.35	10	0.227	1.5	0.637	0.600
w（BN）∶w（B₄C）=20%∶15%	Flake+Block	0.35	63.6	0.227	2.4	0.639	0.756
w（BN）∶w（B₄C）=23%∶12%	Flake+Block	0.35	69.1	0.227	2.5	0.639	0.775

Table 2 Simulation results of thermal conductivity of composite materials

Packing	Packing shape	$V f$	$λ f$ /（W·m^－1·K^－1）	$λ p$ /（W·m^－1·K^－1）	A	$V m$	$λ$ /（W·m^－1·K^－1）
B₄C	Block	0.25	10	0.227	1.5	0.637	0.432
B₄C	Block	0.35	10	0.227	1.5	0.637	0.600
w（BN）∶w（B₄C）=20%∶15%	Flake+Block	0.35	63.6	0.227	2.4	0.639	0.756
w（BN）∶w（B₄C）=23%∶12%	Flake+Block	0.35	69.1	0.227	2.5	0.639	0.775

Fig.5 Thermal conductivity of BN and B4C with different mass ratios

Fig.6 Variations in external and internal temperatures with time during curing process for composites with low （A） and high （B） thermal conductivities. Inserts are the corresponding pictures of prepared samples

Fig.7 Effect of pouring amount （A） and mold material （B） on curing temperature of the system

Table 3 Properties of prepared composite

No.	Performance	Test data	Standard
1	Glass transition temperature/℃	161	GBT 19466.2-2004
2	Temperature of deflection under load/℃	159.1	GB/T 1634.1-2004
3	Thermal decomposition temperature/℃	325	GB/T 27761-2011
4	Weightlessness rate at 180 ℃ for 15 days/%	0.55	GB/T 7141-2008
5	Thermal conductivity/（W·K^-1·m^-1）	0.918	GB/T 22588-2008
6	Compressive strength/MPa	102	GB/T 1041-2008
7	Modulus of compression/GPa	4.5	GB/T 1041-2008
8	Tensile strength/MPa	50	GB/T 1040.1-2006
9	Tensile modulus/GPa	5.1	GB/T 1040.1-2006
10	Bending strength/MPa	78	GB/T 9341-2008
11	Impact strength/MPa	11.67	GB/T 1843-2008
12	Density/（g·cm^-3）	1.458	GB/T 1033.1-2008
13	Fast neutron shielding factor （²⁵²Cf，40 mm）/%	2.56	—
14	Thermal neutron shielding rate （²⁵²Cf，40 mm）/%	99.98	—

Fig.8 Samples prepared by pouring/curing at room temperature

References 23

1	蔡永成，刘学宇，蔡永军，等. 核辐射危害及核辐射屏蔽材料研究现状［J］. 粉末冶金工业， 2023， 33（2）： 96-102.
	CAI Y C， LIU X Y， CAI Y J， et al. Radiation hazard and research status of radiation shielding materials［J］. Powder Metall Ind， 2023， 33（2）： 96-102.
2	付春亮. 辐射防护材料的研究［J］. 科技资讯， 2022， 20（13）： 58-60.
	FU C L. Research on radiation protection materials［J］. Sci Technol Inf， 2022， 20（13）： 58-60.
3	陈秋雨，张城皓，曹可，等. 高分子基辐射防护材料研究进展［J］. 材料导报， 2022， 36（S1）： 541-544.
	CHEN Q Y， ZHANG C H， CAO K， et al. Research progress of polymer based radiation protection materials［J］. Mater Rev， 2022， 36（S1）： 541-544.
4	李哲夫，薛向欣. 含硼矿物及环氧树脂复合材料的中子屏蔽性能［J］. 原子能科学技术， 2011， 45（2）： 223-229.
	LI Z F， XUE X X. Neutron shielding properties of boron containing mineral and epoxy resin composites［J］. At Energy Sci Technol， 2011， 45（2）： 223-229.
5	邵世鹏，王玉杰，董涵. 室温固化环氧树脂浇注料的研究［J］. 黑龙江科技信息， 2015（16）： 115.
	SHAO S P， WANG Y J， DONG H. Study on room temperature curing epoxy resin castable［J］. Heilongjiang Sci Technol Inf， 2015（16）： 115.
6	于平，张国亮，张连红，等. 室温快固化环氧树脂固化剂研究进展［J］. 当代化工， 2012， 41（2）： 173-176.
	YU P， ZHANG G L， ZHANG L H， et al. Research progress in room temperature fast-curing epoxy resin curing agents［J］. Contemp Chem Ind， 2012， 41（2）： 173-176.
7	张春玲，那辉，牟建新，等. 含联苯结构的环氧树脂固化性能的研究［J］. 高等学校化学学报， 2004（9）： 1756-1758.
	ZHANG C L， NA H， MOU J X， et al. Study on curing property of epoxy resin containing biphenyl structure ［J］. Chem J China Univ， 2004（9）： 1756-1758.
8	翁秋燕，刘灿培，陈明锋，等. 含氨基苯并噻唑刚性链节环氧树脂材料的制备及热稳定性研究［J］. 福建师范大学学报（自然科学版）， 2015， 31（4）： 63-67.
	WENG Q Y， LIU C P， CHEN M F， et al. Preparation and thermal stability of epoxy resin with aminobenzothiazole［J］. J Fujian Norm Univ （Nat Sci Ed）， 2015， 31（4）： 63-67.
9	毛建，王钧，段华军. 多官能度环氧树脂对共混体系耐热性能的影响［J］. 热固性树脂， 2006（1）： 16-17， 20.
	MAO J， WANG J， DUAN H J. Effect of multi-functional epoxy resin on heat resistance of blend system［J］. Thermosetting Resin， 2006（1）： 16-17， 20.
10	李栓，杜宇，张宝艳. 苯并噁嗪树脂改性环氧树脂胶黏剂的阻燃性能［J］. 合成树脂及塑料， 2023， 40（2）： 23-26.
	LI S， DU Y， ZHANG B Y. Flame retardation of epoxy resin adhesive modified by benzoxazine resin［J］. Synth Resins Plast， 2023， 40（2）： 23-26.
11	刘宁，侯晓，刘津生，等. 不同固化剂复配的低温固化环氧树脂体系性能［J］. 固体火箭技术， 2022， 45（2）： 274-280.
	LIU N， HOU X， LIU J S， et al. Properties of low temperature curing epoxy resin system with different curing agents［J］. Solid Rocket Technol， 2022， 45（2）： 274-280.
12	贾彩霞，梁禄忠，王乾，等. 非活性稀释剂对常温固化环氧树脂性能的影响［J］. 高分子材料科学与工程， 2019， 35（1）： 59-63.
	JIA C X， LIANG L Z， WANG Q， et al. Effect of inactive diluent on properties of epoxy resin cured at room temperature［J］. Polym Mater Sci Eng， 2019， 35（1）： 59-63.
13	冉德龙，谢建军，黄凯，等. 室温固化的耐高温环氧胶粘剂［J］. 材料研究进展， 2011： 284-286.
	RAN D L， XIE J J， HUANG K， et al. High temperature resistance of epoxy adhesives under the room-temperature curing［J］. Adv Mater Res， 2011： 284-286.
14	王珂，虞鑫海，徐永芬. 耐高温环氧树脂胶粘剂的研究进展［J］. 粘接， 2013， 34（2）： 63-65.
	WANG K， YU X H， XU Y F. Research progress of epoxy resin adhesives resistant to high temperature［J］. Adhesion， 2013， 34（2）： 63-65.
15	孙曼灵. 环氧树脂应用原理与技术［M］. 北京：机械工业出版社， 2002： 4-5.
	SUN M L. Application of the principles and techniques of epoxy resin［M］. Beijing： China Machine Press， 2002： 4-5.
16	张庆思. 环氧树脂固化反应表观活化能的研究［J］. 涂料工业， 1996（3）： 1-3， 45.
	ZHANG Q S. Study on the apparent activation energy of epoxy resin curing reaction［J］. Coat Ind， 1996（3）： 1-3， 45.
17	杨帆，粟俊华，胡亚坤，等. 环氧封端聚苯醚/环氧树脂共混体系的固化动力学研究［J］. 塑料科技， 2023， 51（4）： 54-58.
	YANG F， SU J H， HU Y K， et al. Study on curing kinetics of epoxy terminated polyphenylene ether/epoxy resin blends［J］. Plast Sci Technol， 2023， 51（4）： 54-58.
18	路易斯，尼尔森. 颗粒填充复合材料的动态力学性能［J］. 高分子应用科学杂志， 1970， 14（6）： 1449-1471.
	LEWIS T B， NIELSEN L E. Dynamic mechanical properties of particulate-filled composites［J］. J Appl Polym Sci， 1970， 14（6）： 1449-1471.
19	郝鲁阳，温变英，张宜鹏. 填料形状对聚酰胺6基复合材料导热性能的影响［J］. 中国塑料， 2017， 31（11）： 35-40.
	HAO L Y， WEN B Y， ZHANG Y P. Effect of filler shape on thermal conductivity of polyamide［J］. China Plast， 2017， 31（11）： 35-40.
20	冯伟，李伟. 填充型导热绝缘聚合物基复合材料的研究进展［J］. 炭素， 2017（3）： 5-11.
	FENG W， LI W. Research progress of filled thermal insulation polymer matrix composites ［J］. Carbon， 2017（3）： 5-11.
21	马传国，容敏智，章明秋. 聚合物基复合材料导热模型及其应用［J］. 宇航材料工艺， 2003（3）： 1-4.
	MA C G， RONG M Z， ZHANG M Q. Thermal conductivity model of polymer matrix composites and its application［J］. Aerosp Mater Technol， 2003（3）： 1-4.
22	吕勇，罗世永，许文才. 导热绝缘高分子复合材料中填料的研究进展［J］. 北京印刷学院学报， 2008， 16（2）： 76-78.
	LV Y， LUO S Y， XU W C. Research progress of fillers in heat conduction and insulationv polymer composites‍［J］. J Beijing Inst Print Technol， 2008， 16（2）： 76-78.
23	陶文铨. 传热学［M］. 第五版. 北京：高等教育出版社， 2019： 5-15.
	TAO W Q. Heat transfer［M］. 5nd ed. Beijing： Higher Education Press， 2019： 5-15.

[1]	Peng-Hui FAN, Jie LIU, Sheng-Hui LOU, Tao TANG. Research Progress on Synergists of Phosphorous Flame Retardants in Epoxy Resin [J]. Chinese Journal of Applied Chemistry, 2023, 40(5): 653-665.
[2]	Yong-Xin TANG, Li-Wu NIE. Effect of Epoxy Resin Content on the Performance of Luminous Resin Permeable Concrete [J]. Chinese Journal of Applied Chemistry, 2022, 39(11): 1665-1671.
[3]	YOU Geyun, FENG Bin, FAN Fangfang, YANG Changjie, LIANG Cong. Synthesis of Phosphorus-Nitrogen Synergistic Flame-Retardant Compounds with Imide Structure and Their Flame Retardant Effect on Epoxy Resin [J]. Chinese Journal of Applied Chemistry, 2020, 37(2): 144-154.
[4]	ZHANG Lu, WANG Haichang, LI Hua, WANG Huijun, HUI Linhai, PENG Meiling, ZHU Yutian. Progress of Recycling of Carbon Fiber/Resin Composites via Supercritical Fluid [J]. Chinese Journal of Applied Chemistry, 2020, 37(12): 1357-1363.
[5]	HOU Chengmin,LI Na,DONG Haitao,KOU Yanping. Preparation and Performance of Hybrid Superhydrophobic Materials from Fluorinated Epoxy Resin and Silica Nanoparticles [J]. Chinese Journal of Applied Chemistry, 2019, 36(7): 798-806.
[6]	ZHANG Lili, DING Huimin, ZHANG Jitang, XU Donghua, LI Zhifeng. Thermal Conductivity and Flame Retardancy of Carbon Nanotube Modified Epoxy Resin [J]. Chinese Journal of Applied Chemistry, 2017, 34(1): 46-53.
[7]	CHEN Mingfeng, LU Qingxin, LIU Canpei, LIN Jinhuo. Preparation and Thermal Property of Epoxy Resin Containing Aromatic Thiazole Groups [J]. Chinese Journal of Applied Chemistry, 2016, 33(3): 293-298.
[8]	ZHANG Huanhuan, XU Donghua, GUAN Dongbo, YAO Weiguo, SHI Tongfei. The Curing Process of Epoxy Resin Tooling Board for Slush Mold at Different Temperature [J]. Chinese Journal of Applied Chemistry, 2016, 33(3): 299-306.
[9]	HU Sanming, WEI Wei, YANG Tianbo, ZHENG Changmei, ZHENG Chunbai, DENG Pengyang. Properties of a New Type Heat-Resistant System of Epoxy Resin Cured at Room Temperature [J]. Chinese Journal of Applied Chemistry, 2016, 33(2): 175-180.
[10]	BAI Tian, GUO Anru, LI Ruijie, LIU Chang, XIAO Dehai. Effect of Diluent on Performances of High-Temperature Resistance Epoxy Resin [J]. Chinese Journal of Applied Chemistry, 2016, 33(12): 1401-1407.
[11]	MA Yuqin, ZHENG Changmei, YANG Tianbo, WEI Wei, LIU Meihua, ZHENG Chunbai, DENG Pengyang, GAO Ying. Reaction Characteristics of Epoxy Resins E-51 Cured by 1-Hexyl-3-Methyl Imidazole Iron Tetrachloride Salt [J]. Chinese Journal of Applied Chemistry, 2015, 32(6): 636-640.
[12]	LI Dan, SU Xiaosheng, ZHANG Chi. Application of Two-Dimensional Fourier Transform Infrared Correlation Spectroscopy on Dicyandiamide-Epoxy Network [J]. Chinese Journal of Applied Chemistry, 2015, 32(11): 1275-1282.
[13]	LIU Changling*, YANG Ning, ZHANG Zeyu. Preparation and Properties of Al₂O₃-Modified Epoxy Resin for Electronic Packaging [J]. Chinese Journal of Applied Chemistry, 2013, 30(12): 1417-1422.
[14]	WANG Yiming1,2, LIU Jie2, WU Guangfeng1, TANG Tao2. Recycling of Carbon Fiber Reinforced Epoxy Resin Cured with Anhydride in Subcritical Water [J]. Chinese Journal of Applied Chemistry, 2013, 30(06): 643-647.
[15]	ZHONG Yinhua, LUO Yan*, ZENG Jian, WEI Yinglin, WU Yehui. Epoxy Resin Toughened by Polyester Hot Melt Adhesive [J]. Chinese Journal of Applied Chemistry, 2012, 29(07): 745-750.

High Temperature Resistant Epoxy Resin-Based Composites by Casting Process for Neutron Shielding

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 23

Related Articles 15

Recommended Articles

Metrics

Comments