金属氧化物对膨胀阻燃涂层耐火及成炭性能的影响

doi:10.15541/jim20130686

摘要/Abstract

摘要：

金属氧化物(MO)可显著影响膨胀阻燃体系的热解成炭过程, 进而改善膨胀阻燃涂层的耐火性能。将Fe₂O₃、ZnO、TiO₂分别添加到双环笼状磷酸酯膨胀阻燃环氧涂层中, 研究了MO对涂层耐火及成炭性能的影响规律。燃烧背温测试结果表明, MO可产生显著的协效耐火作用, 三种MO对耐火性能的增效能力为Fe₂O₃>ZnO>TiO₂。热失重(TGA), 激光拉曼光谱(LRS)和X射线光电子能谱(XPS)分析表明, MO促进了残炭的耐高温氧化性能及类石墨化程度的提高, 增加了涂层的高温残炭量, 三种MO提升涂层成炭性能的能力为Fe₂O₃>ZnO>TiO₂。

关键词: 金属氧化物, 双环笼状磷酸酯, 膨胀阻燃, 环氧涂层

Abstract:

Metal oxides (MO) can remarkably affect the char formation of intumescent flame retardants (IFR) during thermal decomposition, thereby improving the fire resistance property of IFR coatings. In present work, Fe₂O₃, ZnO and TiO₂ were separately incorporated with caged bicyclic phosphates based IFR in epoxy coating, and their effects on fire resistance and char formation of the IFR coating were investigated. Back temperature test results showed that MO worked synergistically on improving fire resistance of the coating and their effectiveness of improvement followed the trend of Fe₂O₃>ZnO>TiO₂. Thermogravimetric analysis (TGA), laser Raman spectroscopy (LRS) and X-ray photoelectron spectroscopy (XPS) results revealed that MO promoted the formation of pseudo-graphic char with improved thermal stability which still survived at high temperature, and their effectiveness of promotion also followed the trend of Fe₂O₃>ZnO>TiO₂.

Key words: metal oxides, caged bicyclic phosphates, intumescent flame retardancy, epoxy coating

中图分类号:

TQ132

周友, 刘秀, 王芳, 郝建薇, 杜建新. 金属氧化物对膨胀阻燃涂层耐火及成炭性能的影响[J]. 无机材料学报, 2014, 29(9): 972-978.

ZHOU You, LIU Xiu, WANG Fang, HAO Jian-Wei, DU Jian-Xin. Effect of Metal Oxides on Fire Resistance and Char Formation of Intumescent Flame Retardant Coating[J]. Journal of Inorganic Materials, 2014, 29(9): 972-978.

图/表 11

参考文献 33

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No.	Sample	Fire resistance time/s	V_300℃^a/(℃•s^-1)	V_400℃/(℃•s^-1)
		t_300℃	t_400℃
1	EP/T-IFR	200	1040	1.50	0.38
2	EP/T-IFR/2.3wt% Fe₂O₃	230	2200	1.30	0.18
3	EP/T-IFR/3.5wt% Fe₂O₃	280	2360	1.07	0.17
4	EP/T-IFR/4.5wt% Fe₂O₃	220	2010	1.36	0.20
5	EP/T-IFR/2.3wt% ZnO	320	1780	0.94	0.22
6	EP/T-IFR/3.5wt% ZnO	340	2140	0.88	0.19
7	EP/T-IFR/4.5wt% ZnO	530	1710	0.57	0.23
8	EP/T-IFR/2.3wt% TiO₂	220	1440	1.36	0.28
9	EP/T-IFR/3.5wt% TiO₂	260	1520	1.15	0.26
10	EP/T-IFR/4.5wt% TiO₂	240	1380	1.25	0.29

No.	Sample	Fire resistance time/s	V_300℃^a/(℃•s^-1)	V_400℃/(℃•s^-1)
		t_300℃	t_400℃
1	EP/T-IFR	200	1040	1.50	0.38
2	EP/T-IFR/2.3wt% Fe₂O₃	230	2200	1.30	0.18
3	EP/T-IFR/3.5wt% Fe₂O₃	280	2360	1.07	0.17
4	EP/T-IFR/4.5wt% Fe₂O₃	220	2010	1.36	0.20
5	EP/T-IFR/2.3wt% ZnO	320	1780	0.94	0.22
6	EP/T-IFR/3.5wt% ZnO	340	2140	0.88	0.19
7	EP/T-IFR/4.5wt% ZnO	530	1710	0.57	0.23
8	EP/T-IFR/2.3wt% TiO₂	220	1440	1.36	0.28
9	EP/T-IFR/3.5wt% TiO₂	260	1520	1.15	0.26
10	EP/T-IFR/4.5wt% TiO₂	240	1380	1.25	0.29

Sample	T_i /℃	△T_i /℃	CR_300℃ /%	△CR^b_300℃/%	CR_700℃ /%	△CR_700℃/%
Sample	Calcd./Exp.	△T_i /℃	Calcd./Exp.	△CR^b_300℃/%	Calcd./Exp.	△CR_700℃/%
EP/T-IFR	-/238	-	-/86	-	-/27	-
EP/T-IFR/3.5wt% Fe₂O₃	242/271	29	87/91	4	29/39	10
EP/T-IFR/3.5wt%ZnO	242/270	28	87/93	6	29/36	7
EP/T-IFR/3.5wt% TiO₂	242/268	26	87/89	2	29/32	3

Sample	T_i /℃	△T_i /℃	CR_300℃ /%	△CR^b_300℃/%	CR_700℃ /%	△CR_700℃/%
Sample	Calcd./Exp.	△T_i /℃	Calcd./Exp.	△CR^b_300℃/%	Calcd./Exp.	△CR_700℃/%
EP/T-IFR	-/238	-	-/86	-	-/27	-
EP/T-IFR/3.5wt% Fe₂O₃	242/271	29	87/91	4	29/39	10
EP/T-IFR/3.5wt%ZnO	242/270	28	87/93	6	29/36	7
EP/T-IFR/3.5wt% TiO₂	242/268	26	87/89	2	29/32	3

Sample	T_i /℃	△T_i /℃	CR_700℃ /%	△CR_700℃/%
Sample	Calcd./Exp.	△T_i /℃	Calcd./Exp.	△CR_700℃/%
EP	-/123	-	-/5.7	-
EP/5wt%Fe₂O₃	125/183	58	10.4/15.9	5.5
EP/5wt%ZnO	125/186	61	10.4/18.7	8.3
EP/5wt%TiO₂	125/172	47	10.4/12.6	2.2