改性玄武岩/水凝胶复合涂层对木材阻燃性能的影响

王驰; 刘静; 张梦颖; 袁光明; 葛海林

改性玄武岩/水凝胶复合涂层对木材阻燃性能的影响

王驰^{1, 2},
刘静¹,
张梦颖¹,
袁光明^1, ,,
葛海林²

1.
中南林业科技大学　材料科学与工程学院, 长沙 410004
2.
圣奥科技股份有限公司, 杭州 311215

基金项目: 国家自然科学基金(32171708、31770606)；国家重点研发计划项目(2019YFE0114600)

详细信息

通讯作者:
袁光明，博士，教授，博士生导师，研究方向为生物质复合材料、木材功能性改良，　E-mail：ygm@csuft.edu.cn

中图分类号: S785; TQ127.1+1; TB332
计量
- 文章访问数: 53
- HTML全文浏览量: 24
- 被引次数: 0
出版历程
- 收稿日期: 2024-04-26
- 修回日期: 2024-06-15
- 录用日期: 2024-06-21
- 网络出版日期: 2024-07-03

Modified basalt/hydrogel composite coating study on the influence of flame retardancy of wood

1.
College of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha 410004, China
2.
Sunon Technology Co., Ltd, Hangzhou 311215, China

Funds: National Natural Science Foundation of China (No.32171708; No.31770606); National Key Research and Development Program of China (No.2019TFE0114600)

摘要

摘要: 以加入了次磷酸铝(AHP)的聚乙烯醇(PVA)/壳聚糖(CS)作为水凝胶基质，经NaOH预处理、KH550接枝改性和植酸金属化合物共沉淀后的玄武岩(BS)作为阻燃填料，制备了BS-PA-Al、BS-PA-Ni和BS-PA-Zn水凝胶阻燃涂层材料。将三种涂层涂覆到木材表面后，分别对其进行了热重测试、锥形量热测试和垂直燃烧实验，分析改性玄武岩/水凝胶复合涂层对木材阻燃和力学性能的影响。结果表明：由于可燃气体的稀释和炭层致密性的增加，BS-PA-Al、BS-PA-Ni和BS-PA-Zn阻燃涂层对木材的阻燃性能有显著地提升；其中，BS-PA-Ni的阻燃性能和机械性能达到最佳，其UL-94测试达V-0级；且相较于空白组木材，残炭率增加至27.3%，其pHRR、THR和TSP分别降低64.2%、32.7%和51.3%；此外，当涂层厚度为300 μm时，其BS-PA-Ni的力学性能(抗拉强度)增加至80.4%，水凝胶在木材上的附着强度达到3.4 MPa。
- 水凝胶涂层 /
- 阻燃 /
- 玄武岩 /
- 次磷酸铝 /
- 木材
Abstract: BS-PA-Al, BS-PA-Ni and BS-PA-Zn hydrogel flame retardant coating materials were prepared respectively using polyvinyl alcohol (PVA)/chitosan (CS) including aluminum hypophosphite (AHP) as hydrogel matrix, and employing basalt (BS) after NaOH pretreatment, KH550 grafting modification and phytic acid co-precipitation act as flame retardant filler. The effects of modified basalt/hydrogel composite coating on flame retarding and mechanical properties of wood were analyzed by thermogravimetric test, cone calorimetric test and vertical combustion test after coating on wood surface respectively. The results show that, due to the dilution of combustible gas and the increase of carbon layer density, the flame retardant properties of BS-PA-Al, BS-PA-Ni and BS-PA-Zn hydrogel flame retardant coated wood have been significantly improved. Among them, the flame retardant properties and mechanical properties of BS-PA-Ni have reached the best, and its UL-94 test has reached V-0 level. The residual carbon rate increased to 27.3%, while the pHRR, THR and TSP decreased by 64.2%, 32.7% and 51.3%, respectively. In addition, when the thickness of the coating is 300 μm, the mechanical properties (tensile strength) of BS-PA-Ni enhanced to 80.4%, and the adhesion strength of the hydrogel on the wood reaches 3.4 MPa.
- hydrogel coating /
- flame retardant /
- basalt /
- aluminum hypophosphite /
- wood

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图 1 改性玄武岩的制备工艺

Figure 1. Preparation process of modified basalt

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图 2 样品的SEM图：BS(a)；NaOH蚀刻后的BS(b)；BS-PA-Al(c)；BS-PA-Al的和EDX能谱图(d)；BS-PA-Ni(e)；BS-PA-Ni的EDX能谱图(f)；BS-PA-Zn(g)；BS-PA-Zn的EDX能谱图(h)

Figure 2. SEM of modified basalt: unmodified basalt (a); NaOH etched basalt (b); Aluminum phytate modified basalt (c); Aluminum phytate modified basalt and element distribution (d); Nickel phytate modified basalt (e); Nickel phytate modified basalt and element distribution (f); Zinc phytate modified basalt (g); Zinc phytate modified basalt and element distribution (h);

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图 3 改性玄武岩傅里叶红外光谱图

Figure 3. FTIR diagram of modified basalt

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图 4 水凝胶阻燃涂料热重曲线：热重曲线(a)和热重微分曲线(b)

Figure 4. Thermogravimetric curves of hydrogel flame retardant coating: TG (a) and DTG (b)

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图 5 水凝胶阻燃涂料的热释放速率(a)、热释放总量(b)、产烟速率(c)以及产烟总量(d)

Figure 5. HRR(a), THR(b), SPR(c) and TSP(d) of hydrogel flame retardant coating

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图 6 水凝胶阻燃涂料的力学性能：未涂覆和涂覆木材的抗拉强度(a)和涂层附着力测试图(b)

Figure 6. Mechanical properties of hydrogel flame retardant coating: Tensile strength (a) and coating adhesion test diagram (b) of uncoated and coated wood

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图 7 水凝胶阻燃涂料的阻燃机制

Figure 7. Hydrogel flame retardant coating flame retardant mechanism diagram

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表 1 水凝胶阻燃涂料配方

Table 1. Hydrogel flame retardant coating formula

Sample	Hydrogel/wt%	AHP/wt%	Modified BS/wt%
Control	100	0	0
BS-PA-Al	90	3	7
BS-PA-Ni	90	3	7
BS-PA-Zn	90	3	7
Note: Hydrogel—The amount of hydrogel in the composite coating; AHP—The amount of aluminum hypophosphite in the composite coating; Modified BS—The amount of modified basalt in the composite coating.

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表 2 复合涂料的主要热重分析数据

Table 2. Main TGA data of composite coatings

Sample	T_10%/°C	T_50%/°C	Residue/%
Control	164.36	327.91	3.12
BS-PA-Al	129.07	339.87	22.4
BS-PA-Ni	123.64	382.43	27.3
BS-PA-Zn	116.88	351.55	20.8
Notes: T_10%—Temperatureat5% mass loss; T_50%—Temperature at5% mass loss; Residue—Residual carbon content.

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表 3 水凝胶阻燃涂料锥形量热主要数据

Table 3. Hydrogel flame retardant CCT main data

Sample	TTI/s	pHRR/ (kW·m⁻²)	THR/ (MJ·m⁻²)	TSP/ m²
Pure wood	12	572.90	44.17	1.99
Control	47	294.50	35.80	2.91
BS-PA-Al	22	210.51	33.51	0.89
BS-PA-Ni	27	205.38	29.74	0.97
BS-PA-Zn	21	240.68	35.44	1.37
BS-PA-Ni (dry)	17	397.90	39.14	3.16
Notes: TTI—The time to ignition of wood; pHRR—Peak heat release rate; THR—Total heat release; TSP—Total smoke release.

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表 4 水凝胶阻燃涂料的垂直燃烧数据

Table 4. Vertical combustion data of hydrogel flame retardant coating

Sample	T₁/s	T₂/s	UL-94	Dripping or not
Pure wood	/	/	NR	Yes
Control	2	21	V-1	No
BS-PA-Al	0	0	V-0	No
BS-PA-Ni	0	0	V-0	No
BS-PA-Zn	3	13	V-1	No
Notes: T₁—The first fire of wood; T₂—The second fire of wood; UL-94—UL-94 combustion rating of wood; Dripping or not—Whether the coating drips during wood burning.

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