环氧化天然橡胶改性石墨烯-炭黑/天然橡胶复合材料的制备及性能

段雯雯; 王建军; 辛振祥; 王洪振

doi:10.13801/j.cnki.fhclxb.20191125.002

环氧化天然橡胶改性石墨烯-炭黑/天然橡胶复合材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20191125.002

青岛科技大学　橡塑材料与工程教育部重点实验室，青岛 266042

基金项目: 国家自然科学基金(51703110)；山东省自然科学基金(ZR2017LB015)；中国热带农业科学院开放课题(RRI-KLOF201705)

详细信息

通讯作者:
王洪振，博士，讲师，研究方向为橡胶绿色及高性能加工　E-mail：qustwhz@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2019-07-28
- 录用日期: 2019-10-01
- 网络出版日期: 2019-11-25
- 刊出日期: 2020-07-15

Preparation and properties of epoxidized natural rubber modified graphene-carbon black/natural rubber composites

Key Laboratory of Rubber Materials and Engineering, Ministry of Education, Qingdao University of Science and Technology, Qingdao 266042, China

摘要

摘要: 以环氧化天然橡胶(ENR)为界面改性剂，制备了石墨烯-炭黑/天然橡胶-ENR(GR-CB/NR-ENR)复合材料，研究了ENR用量对GR-CB/NR-ENR复合材料的加工性能、力学性能和动态力学性能的影响。结果表明，ENR的加入可以改善GR-CB/NR-ENR复合材料的加工性能及CB粒子在天然橡胶基体中的分散性，增加GR与NR的相容性，增强填料与NR基体间的界面相容性，同时改善GR-CB/NR-ENR硫化胶的动态力学性能、物理性能和耐老化性能。当ENR添加量为6 wt%时，GR-CB/NR-ENR复合材料撕裂强度和拉伸强度最高，硫化胶耐老化性最好。随着ENR含量的增加，GR-CB/NR-ENR复合材料的压缩疲劳温度先升高后降低；随着应变的不断增大，GR-CB/NR-ENR复合材料的储能模量G'不断减小，损耗因子tanδ先增大后减小；动态模量随着应变的增加急剧下降。
- 石墨烯 /
- 环氧化天然橡胶 /
- 复合材料 /
- 天然橡胶 /
- 微观结构
Abstract: The epoxidized natural rubber(ENR) was an interfacial modifier for the preparation of graphene-carbon black/natural rubber-ENR(GR-CB/NR-ENR) composites. The effects of ENR dosage on the processing properties, mechanical properties and dynamic mechanical properties of GR-CB/NR-ENR composites were studied. The results show that the addition of ENR can improve the processing properties of GR-CB/NR-ENR composites and the dispersion of CB particles in NR matrix. Increasing the compatibility of GR with NR, the interfacial compatibility between the filler and the NR matrix is enhanced, the dynamic mechanical properties, physical properties and aging resistance are improved. When 6 wt% ENR is added, the GR-CB/NR-ENR composite has the highest tear strength and tensile strength, and the GR-CB/NR-ENR vulcanized rubber has the best aging resistance. As the ENR content increases, the compression fatigue temperature of the GR-CB/NR-ENR composite increases first and then decreases; As the strain increases, the storage modulus G' of the GR-CB/NR-ENR composite decreases continuously, and the loss factor tanδ shows a phenomenon of increasing first and then decreasing, while the dynamic modulus drops sharply with increasing strain.
- graphene /
- epoxidized natural rubber /
- composites /
- natural rubber /
- micro structure

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图 1 GR-CB/NR-ENR复合材料的储能模量G′、损耗模量G′′、损耗因子tanδ与应变之间的关系

Figure 1. Relationships between storage modulus G', loss modulus G", loss factor tanδ and strain of GR-CB/NR-ENR composites

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图 2 GR-CB/NR-ENR复合材料断面的SEM图像

Figure 2. SEM images of fracture surface of GR-CB/NR-ENR composites

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表 1 石墨烯-炭黑/天然橡胶-环氧化天然橡胶(GR-CB/NR-ENR)复合材料组分含量(与NR质量比)

Table 1. Component contents of graphene-carbon black/ natural rubber-epoxidized natural rubber(GR-CB/NR-ENR) composite (mass ratio to NR)

Number	1^#	2^#	3^#	4^#
NR/%	100	100	100	100
Stearic acid/%	2	2	2	2
Zinc oxide/%	4	4	4	4
Diphenyl-hydrazine/%	0.6	0.6	0.6	0.6
2,2'-dibenzothiaz-oledisulfde/%	1.2	1.2	1.2	1.2
Anti-aging agent 4010/%	3	3	3	3
CB/%	30	30	30	30
GR/%	4	4	4	4
ENR/%	0	3	6	9

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表 2 GR-CB/NR-ENR复合材料的硫化特性

Table 2. Vulcanization characteristics of GR-CB/NR-ENR composites

Number	1^#	2^#	3^#	4^#
M_L/(dN·m)	1.69	1.48	1.39	1.83
M_H/(dN·m)	12.29	12.19	10.26	10.51
M_H–M_L/(dN·m)	10.6	10.71	8.87	8.68
t₁₀/min	1.33	1.32	1.40	0.70
t₉₀/min	4.59	4.59	4.58	3.53
Notes: M_L—Minimum torque; M_H—Maximum torque; t₁₀—Scorching time; t₉₀—Process vulcanization time.

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表 3 GR-CB/NR-ENR复合材料的力学性能

Table 3. Mechanical properties of GR/CB/NR composites

Number	1^#	2^#	3^#	4^#
Shore A hardness	66	66	65	65
Tear strength/ (kN·m⁻¹)	47.17	53.02	47.56	49.49
Tensile strength/MPa	25.88	26.50	27.12	26.08
Elongation at break/%	539.8	619.05	675.1	646.7
100% fixed stress/MPa	2.32	2.19	1.45	1.66
300% fixed stress/MPa	10.67	10.23	7.05	8.27
Resilience	68.10	65.44	64.85	62.99

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表 4 GR-CB/NR-ENR复合材料老化后的拉伸性能

Table 4. Tensile properties of GR-CB/NR-ENR composites after aging

Number	1^#	2^#	3^#	4^#
Tensile strength/ MPa	16.17	17.92	22.37	21.49
Elongation at break/%	352.1	388.0	510.6	431.5
100% fixed stress/MPa	3.39	3.53	2.77	2.77
300% fixed stress/MPa	13.55	14.09	11.71	12.03
Aging coefficient	0.41	0.42	0.62	0.54

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表 5 GR-CB/NR-ENR复合材料的压缩疲劳生热性能

Table 5. Compression fatigue heat generation performance of GR-CB/NR-ENR composites

Number	1^#	2^#	3^#	4^#
Compressed fatigue temperature rise/℃	19.8	20.5	22.7	21.6

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表 6 GR-CB/NR-ENR复合材料耐屈挠龟裂性能

Table 6. Flexural crack resistance of GR-CB/NR-ENR composites

Number	1^#	2^#	3^#	4^#
Grade 1 crack (Thousand times)	25	25	25	25
Grade 6 crack (Thousand times)	48	48	50	49

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