填料对过氧化物硫化氟橡胶性能的影响

王珊; 苏正涛; 赵艳芬

doi:10.11868/j.issn.1005-5053.2016.2.007

填料对过氧化物硫化氟橡胶性能的影响

doi: 10.11868/j.issn.1005-5053.2016.2.007

北京航空材料研究院减振降噪材料及应用技术航空科技重点实验室, 北京 100095

基金项目: 中国航空工业集团公司创新基金(2014E62136)

详细信息

通讯作者:
王珊(1988-),女,硕士,主要从事特种橡胶材料的研究,(E-mail)wangshan.05.13@163.com。

中图分类号: TQ333.93
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出版历程
- 收稿日期: 2015-08-07
- 修回日期: 2015-12-22
- 刊出日期: 2016-04-01

Effect of Filler Systems on Properties of Fluororubber Vulcanized by Peroxide

Aviation Key Laboratory of Science and Technology on Material and Application Research for Vibration and Noise Reduction, Beijng Institute of Aeronautical Materials, Beijing 100095, China

摘要

摘要: 研究了纳米无机填料体系对过氧化物硫化氟橡胶硫化特性、力学性能、热空气老化性能、热传导性能以及热稳定性能的影响,结果表明:与BaSO₄,BN和R930相比,三种不同结构形态的碳纳米材料明显延长了氟橡胶的正硫化时间;当硫化橡胶硬度级别相同时,多壁碳纳米管CNTs、石墨和N990对过氧化物硫化氟橡胶补强效果显著,其中CNTs的补强效率最高,添加CNTs可提高氟橡胶的撕裂强度,但严重损害其压缩永久变形性能;添加石墨和N990的氟橡胶可以获得更好的耐空气老化性能和耐高温压缩性能,添加R930耐高温压缩性能最好;石墨和BN有利于氟橡胶的导热性;添加BaSO₄的氟橡胶热失重分解温度最高,且质量损失率最小。
- 氟橡胶 /
- 纳米无机填料 /
- 硫化特性 /
- 力学性能 /
- 热空气老化性能 /
- 热传导性能 /
- 热稳定性能 /
- 过氧化物
Abstract: The effect of nano inorganic filler systems on curability, mechanical property, thermal aging property, thermal conductivity and thermal stability of peroxide vulcanization of fluororubber was investigated. The results show that T90 of fluororubbers is delayed with the addition of different morphology of carbon nano-materials compared with BaSO₄, BN and R930. The mechanical property and reinforcing efficiency of fluoroelastomer filled by CNTs, graphite and N990 are increased more than the others, when all the vulcanized rubbers possesse the same hardness. CNTs shows the best reinforcing efficiency. Inorganic filler CNTs can increase the tear strength, but it can also result in a higher compression set. Thermal aging property and compression set resistance of fluororubber filled with Graphite and N990 have better performance. Compression set of fluororubber is minimum with the addition of rutile type TiO₂(R930). Graphite and BN are benefit to thermal conductivity. Fluororubber with BaSO₄ possesses the highest decomposition temperature and the smallest mass loss.
- fluoroelastomer /
- peroxide /
- nano inorganic fillers /
- vulcanizing property /
- mechanical property /
- thermal aging property /
- thermal conductivity /
- thermal stability

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图 1 无机填料体系对氟橡胶硫化特性的影响

Figure 1. Effect of inorganic filler systems on curability of FKM

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图 2 CNTs填充氟橡胶体系的断面电镜图

Figure 2. Section morphology image of CNTs/FKM composite

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图 3 无机填料体系对氟橡胶压缩永久变形的影响

Figure 3. Effect of inorganic filler systems on compression set of FKM

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图 4 无机填料对氟橡胶热导率的影响

Figure 4. Effect of inorganic filler systems on thermal conductivity of FKM

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图 5 石墨(a)、六方氮化硼(b)^[8]和碳纳米管(c)结构示意图

Figure 5. Molecular structure of graphite (a)，hexagonal boron nitride (b)^[8] and CNTs (c)

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图 6 不同填充体系氟橡胶的热失重曲线

Figure 6. TG curves of FKM with different filler systems

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表 1 基本配方

Table 1. Basic formulation

Formulation	P459 (phr)	BaSO₄ (volume fraction/%)	BN (volume fraction/%)	R930 (volume fraction/%)	CNTs (volume fraction/%)	Graphite (volume fraction/%)	N990 (volume fraction/%)	TAIC (phr)	DBPH (phr)
1	100	13						3	1.5
2	100		10.5					3	1.5
3	100			13.4				3	1.5
4	100				6.8			3	1.5
5	100					12		3	1.5
6	100						36	3	1.5

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表 2 不同填料填充氟橡胶的硫化参数

Table 2. Effect of different filler systems on the curing processing parameters of FKM

Sample	M_L/dNm	M_H/dNm	t₁₀/min	t₉₀/min
BaSO₄	0.21	42.53	2.31	6.20
BN	0.23	47.55	2.32	6.22
R930	0.33	46.41	2.30	5.81
CNTs	1.06	57.12	2.66	10.14
Graphite	0.18	38.94	2.62	8.92
N990	0.30	44.54	2.52	8.00

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表 3 无机填料体系对氟橡胶力学性能的影响

Table 3. Effect of inorganic filler systems on mechanical properties of FKM

Sample	Hardness(Shore A)	100% Tensile strength/MPa	Tensile strength/MPa	Elongation /%	Tear strength/ (kN·m^-1)
BaSO₄	77	7	14.5	202	13
BN	80	9.8	14.7	189	17
R930	77	10.6	13.5	133	16
CNTs	82	14.8	19.4	159	23
Graphite	80	18.6	20.7	152	19
N990	81	11.8	18.5	170	16

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表 4 无机填料对氟橡胶老化性能的影响(250 ℃/24 h in air)

Table 4. Effect of inorganic filler systems on thermal aging properties of FKM(250 ℃/24 h in air)

Sample	Hardness change (Shore A)	Tensile strength change/%	Elongation change/%
BaSO₄	+1	+35.2	-4.0
BN	+2	+15.8	+2.6
R930	+1	+42.2	+19.5
CNTs	+2	+14.4	+1.3
Graphite	+2	0.0	-9.9
N990	+2	+6.4	+13.3

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表 5 不同填料填充氟橡胶的热失重数据

Table 5. TG data of FKM with different filler systems

Sample	T_5% /℃	T_10% /℃	T_20% /℃	T_50% /℃	Δm_{650 ℃}/%
BaSO₄	410	429	461	483	73
BN	404	420	452	476	85.14
R930	406	420	447	471	83.41
CNTs	399	416	451	474	95.27
Graphite	405	422	457	476	83.39
N990	407	421	454	475	97.36
注：T_5%，T_10%，T_20%，T_50%，Δm_{650 ℃}——分别表示质量损失5%，10%，20%，50%时的温度以及650 ℃时的失重率

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