助熔剂对可陶瓷化阻燃室温硫化硅橡胶泡沫性能的影响

商珂; 林贵德; 姜慧婧; 金星; 赵璧; 王俊胜

doi:10.13801/j.cnki.fhclxb.20220915.005

助熔剂对可陶瓷化阻燃室温硫化硅橡胶泡沫性能的影响

doi: 10.13801/j.cnki.fhclxb.20220915.005

商珂¹,
林贵德¹,
姜慧婧²,
金星¹,
赵璧¹,
王俊胜^1, ,

1.
应急管理部天津消防研究所，天津 300381
2.
天津理工大学　环境科学与安全工程学院，天津 300384

基金项目: 国家重点研发计划(2020 YFB0311301；2020 YFB0311300)；应急管理部天津消防研究所基础科研业务费(2022 SJ19)

详细信息

通讯作者:
王俊胜，博士，副研究员，研究方向为防火阻燃材料和消防员个人防护装备　E-mail: wangjunsheng@tfri.com.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-07-29
- 修回日期: 2022-08-24
- 录用日期: 2022-09-02
- 网络出版日期: 2022-09-16
- 刊出日期: 2023-04-20

Effect of flux agents on properties of ceramifiable flame retardant room temperature vulcanized silicone rubber foam

1.
Tianjin Fire Science and Technology Research Institute of MEM, Tianjin 300381, China
2.
School of Environmental Science and Safety Engineering, Tianjin University of Technology, Tianjin 300384, China

Funds: China National Key R&D Program (2020 YFB0311301; 2020 YFB0311300); Basic Scientific Research Expenses of Tianjin Fire Science and Technology Research Institute of MEM (2022 SJ19)

摘要

摘要: 为提升室温硫化硅橡胶泡沫的阻燃性能和耐火性能，本文以不同熔点玻璃粉和硼酸锌为助熔剂，云母粉为耐火填料，制备可陶瓷化阻燃室温硫化硅橡胶泡沫，并研究了不同无机填料种类和配比对硅橡胶泡沫微观形貌、热稳定性、阻燃性能和燃烧行为的影响及不同温度烧蚀下硅橡胶泡沫的陶瓷化行为。结果表明，玻璃粉的引入影响了硅橡胶泡沫的发泡过程，形成了孔径较大的泡沫结构，不利于硅橡胶泡沫阻燃性能、热稳定性、火安全性的提升，但在烧蚀实验中，其能够显著降低硅橡胶泡沫的陶瓷化温度；硼酸锌的引入能够显著提升硅橡胶泡沫的阻燃性能、高温区热稳定性和火安全性，并且硼酸锌与云母粉展现出较好的协同阻燃作用，硅橡胶泡沫的极限氧指数(LOI)最高达到33.2%，并通过垂直燃烧FV-0级，N₂气氛下热重分析测试中900℃时的残炭含量最高可达75.9%，硅橡胶泡沫的热释放和烟释放及烧蚀实验后的质量损失率均得到明显降低，同时，硼酸锌还有助于形成陶瓷状残炭。
- 室温硫化硅橡胶泡沫 /
- 助熔剂 /
- 阻燃性能 /
- 燃烧行为 /
- 陶瓷化性能
Abstract: In order to improve the flame retardancy and fire resistance of room temperature vulcanized (RTV) silicone rubber foam, glass powder and zinc borate as flux agent, and mica powder as refractory filler were used to prepare ceramifiable flame retardant RTV silicone rubber foam. The effects of different types and proportions of inorganic fillers on the micromorphology, thermal stability, flame retardancy and combustion behavior of the silicone rubber foam, as well as the ceramifiable behavior of the silicone rubber foam after ablation at different temperatures were studied. The results show that the introduction of glass powder affects the foaming process of the silicone rubber foam, forming a foam structure with large pore size, which is not conducive to the improvement of the flame retardancy, thermal stability and fire safety performances of the silicone rubber foam. But, glass power can remarkably decrease ceramization temperature of the silicone rubber foam. The introduction of zinc borate greatly improves the flame retardancy, thermal stability in high temperature zone and fire safety performances of the silicone rubber foam. Meanwhile, zinc borate and mica powder show good synergistic flame retardant effect. limiting oxygen index (LOI) value of the silicone rubber foam can reach to 33.2, and it can pass the vertical combustion FV-0 level. Carbon residue of the silicone rubber foam at 900℃ can reach up to 75.9% in thermogravimetric analysis in N₂ atmosphere. The heat release, smoke release of the silicone rubber foam and the mass loss after the ablation experiment are significantly reduced. In addition, zinc borate also contributes to the formation of ceramic carbon residue.
- RTV silicone rubber foam /
- flux agent /
- flame retardancy /
- combustion behavior /
- ceramifiable property

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图 1 可陶瓷化阻燃RTV硅橡胶泡沫的SEM图像

Figure 1. SEM images of the ceramifiable flame retardant RTV silicone rubber foam

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图 2 可陶瓷化阻燃室温硫化硅橡胶泡沫在N₂气氛下的TG (a) 和DTG (b) 曲线

Figure 2. TG (a) and DTG (b) curves of the ceramifiable flame retardant RTV silicone rubber foam under N₂ atmosphere

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图 3 可陶瓷化阻燃室温硫化硅橡胶泡沫在空气气氛下的TG (a) 和DTG (b) 曲线

Figure 3. TG (a) and DTG (b) curves of the ceramifiable flame retardant RTV silicone rubber foam under air atmosphere

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图 4 可陶瓷化阻燃室温硫化硅橡胶泡沫的热释放速率(HRR) (a)、总热释放(THR) (b)、烟释放速率(RSR) (c) 和总烟释放(TSP) (d) 曲线

Figure 4. Heat release rate (HRR) (a), total heat release (THR) (b), rate of smoke release (RSR) (c) and total smoke production (TSP) (d) curves of the ceramifiable flame retardant RTV silicone rubber foam

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图 5 可陶瓷化阻燃室温硫化硅橡胶泡沫锥形量热测试后残炭的数码照片

Figure 5. Digital photographs of carbon residues for the ceramifiable flame retardant RTV silicone rubber foam after cone calorimeter test

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图 6 不同烧蚀温度下可陶瓷化阻燃室温硫化硅橡胶泡沫的SEM图像

Figure 6. SEM images of the ceramifiable flame retardant RTV silicone rubber under different ablation temperatures

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图 7 800℃烧蚀后可陶瓷化阻燃室温硫化硅橡胶泡沫的SEM图像

Figure 7. SEM images of the ceramifiable flame retardant RTV silicone rubber after ablation at 800℃

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表 1 可陶瓷化阻燃室温硫化(RTV)硅橡胶泡沫的配方及极限氧指数(LOI)、垂直燃烧(UL-94)测试结果

Table 1. Formulation, limit oxygen index (LOI) and vertical combustion (UL-94) test results of the ceramifiable flame retardant room temperature vulcanized (RTV) silicone rubber foam

Sample	SRF/wt%	GP/wt%	ZB/wt%	MP/wt%	Melting point of GP/℃	LOI/%	UL-94
SF	100	0	0	0	—	23.4	NR
SF/MP₃₀	70	0	0	30	—	31.8	FV-0
SF/GP400₁₀MP₂₀	70	10	0	20	400	23.4	NR
SF/GP400₁₅MP₁₅	70	15	0	15	400	24.6	NR
SF/GP400₂₀MP₁₀	70	20	0	10	400	23.4	NR
SF/GP500₂₀MP₁₀	70	20	0	10	500	24.0	NR
SF/GP650₂₀MP₁₀	70	20	0	10	650	22.8	NR
SF/GP400₃₀	70	30	0	0	400	26.4	NR
SF/ZB₁₀MP₂₀	70	0	10	20	—	33.2	FV-0
SF/ZB₁₅MP₁₅	70	0	15	15	—	31.8	FV-0
SF/ZB₂₀MP₁₀	70	0	20	10	—	31.0	FV-0
SF/ZB₃₀	70	0	30	0	—	31.6	FV-0
Notes: SRF—Silicone rubber foam; GP—Glass powder; ZB—Zinc borate; MP—Mica powder; SF—Silicone foam; NR—No rating.

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表 2 可陶瓷化阻燃室温硫化硅橡胶泡沫N₂气氛下的热重测试具体数据

Table 2. TGA parameters of the ceramifiable flame retardant RTV silicone rubber foam under N₂ atmosphere

Sample	T_onset/℃	T_max/℃	dW/dT/ (%·min⁻¹)	Residue/%
SF	442.0	576.0	6.36	40.1
SF/MP₃₀	451.7	510.8	2.24	73.0
SF/GP400₁₀MP₂₀	434.9	566.2	6.75	52.8
SF/GP400₁₅MP₁₅	441.4	559.4	10.20	47.5
SF/GP400₂₀MP₁₀	425.2	532.8	7.44	50.4
SF/GP500₂₀MP₁₀	449.7	557.3	10.41	43.7
SF/GP650₂₀MP₁₀	415.8	482.2	11.14	47.7
SF/GP400₃₀	451.6	518.5	20.71	36.4
SF/ZB₁₀MP₂₀	406.2	467.9	2.74	62.9
SF/ZB₁₅MP₁₅	407.7	422.1	1.39	75.9
SF/ZB₂₀MP₁₀	419.1	463.6	1.28	75.0
SF/ZB₃₀	418.4	421.8	1.14	74.1
Note: T_onset, T_max and dW/dT are the onset thermal decomposition temperature, the maximum thermal decomposition temperature and the thermal decomposition rate at the T_max.

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表 3 可陶瓷化阻燃室温硫化硅橡胶泡沫空气气氛下的热重测试具体数据

Table 3. TGA parameters of the ceramifiable flame retardant RTV silicone rubber foam under air atmosphere

Sample	T_onset/℃	T_max/℃	dW/dT/ (%·min⁻¹)	Residue/%
SF	354.4	362.0	9.81	56.9
SF/MP₃₀	378.5	380.7	5.65	76.0
SF/GP400₁₀MP₂₀	377.0	509.3	11.91	52.2
SF/GP400₁₅MP₁₅	375.3	507.5	14.39	46.0
SF/GP400₂₀MP₁₀	373.7	498.9	15.64	42.1
SF/GP500₂₀MP₁₀	363.3	367.2	6.65	64.1
SF/GP650₂₀MP₁₀	376.5	452.8	17.03	42.4
SF/GP400₃₀	369.6	495.8	16.60	40.6
SF/ZB₁₀MP₂₀	374.4	372.3	4.91	80.2
SF/ZB₁₅MP₁₅	379.8	551.9	3.91	73.0
SF/ZB₂₀MP₁₀	376.4	370.5	3.69	79.5
SF/ZB₃₀	367.7	362.1	3.82	81.2

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表 4 可陶瓷化阻燃室温硫化硅橡胶泡沫的锥形量热测试主要数据

Table 4. Burning parameters of the ceramifiable flame retardant RTV silicone rubber foam in cone calorimeter test

Sample	TTI /s	PHRR /(kW·m⁻²)	THR /(MJ·m⁻²)	TTPHRR /s	TSP/(m²·m⁻²)	Residue /%
SF	7	145.0	40.0	170	18.3	52.6
SF/MP₃₀	13	76.6	23.0	30	1.7	79.6
SF/GP400₁₀MP₂₀	15	117.9	35.7	35	16.7	68.3
SF/GP400₁₅MP₁₅	23	133.5	47.7	45	17.6	65.4
SF/GP400₂₀MP₁₀	24	130.7	42.0	45	17.0	60.2
SF/GP500₂₀MP₁₀	14	98.6	36.3	40	11.8	69.2
SF/GP650₂₀MP₁₀	50	167.6	96.0	70	49.5	71.4
SF/GP400₃₀	33	154.0	65.6	50	26.9	66.2
SF/ZB₁₀MP₂₀	16	84.5	25.8	35	3.4	81.8
SF/ZB₁₅MP₁₅	16	73.4	24.5	35	3.2	75.7
SF/ZB₂₀MP₁₀	10	72.2	29.1	30	4.8	81.6
SF/ZB₃₀	14	80.1	30.7	35	7.1	80.5
Notes: TTI—Time to ignition; PHRR—Peak of heat release rate; TTPHRR—Time to PHRR.

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表 5 可陶瓷化阻燃室温硫化硅橡胶泡沫烧蚀后质量损失率

Table 5. Mass loss rate of the ceramifiable flame retardant RTV silicone rubber foam after ablation

Sample	Mass loss/%
Sample	600℃	800℃	1000℃
SF	89.16	75.71	80.33
SF/MP₃₀	45.56	20.45	17.65
SF/GP400₁₀MP₂₀	66.73	67.18	67.52
SF/GP400₁₅MP₁₅	66.02	65.72	64.43
SF/GP400₂₀MP₁₀	62.60	69.52	62.12
SF/GP500₂₀MP₁₀	67.49	66.32	61.66
SF/GP650₂₀MP₁₀	59.73	47.85	51.40
SF/GP400₃₀	64.30	54.52	50.00
SF/ZB₁₀MP₂₀	53.45	32.78	25.61
SF/ZB₁₅MP₁₅	52.07	48.19	26.45
SF/ZB₂₀MP₁₀	35.56	31.63	30.00
SF/ZB₃₀	59.39	35.48	43.35

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