吸水对甲基膦酸二甲酯接枝改性亚麻纤维增强酚醛复合材料的阻燃性能和力学性能的影响

李灼; 李岩; 于涛; 王晶晶

doi:10.13801/j.cnki.fhclxb.20221107.001

吸水对甲基膦酸二甲酯接枝改性亚麻纤维增强酚醛复合材料的阻燃性能和力学性能的影响

doi: 10.13801/j.cnki.fhclxb.20221107.001

同济大学　航空航天与力学学院，上海 200092

基金项目: 科技部重点研发计划(2020YFD1100402-4)

详细信息

通讯作者:
李岩，博士，教授，博士生导师，研究方向为纤维增强树脂基复合材料力学高性能化和耐久性　E-mail: liyan@tongji.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-09-07
- 修回日期: 2022-10-24
- 录用日期: 2022-10-29
- 网络出版日期: 2022-11-07
- 刊出日期: 2023-05-15

Effect of water absorption on the flame retardancy and mechanical properties of flax fiber reinforced phenolic composites grafted with dimethyl methylphosphate

School of Aerospace Engineering and Applied Mechanics, Tongji University, Shanghai 200092, China

Funds: National Key Research and Development Program (2020YFD1100402-4)

摘要

摘要: 近年来，植物纤维增强复合材料因具有绿色环保、高比模量和低成本等优点被国内外广泛关注，改善其易燃和易吸水特性成为这些年的研究热点。为研究阻燃植物纤维增强复合材料的吸水特性，以亚麻纤维增强酚醛复合材料(Flax/Phenolic，FP)为研究对象，利用甲基膦酸二甲酯(Dimethyl methylphosphonate，DMMP)接枝的方法对亚麻纤维进行阻燃处理，探索最佳处理工艺。研究DMMP接枝阻燃复合材料的吸水性及吸水对于复合材料阻燃性能和拉伸性能的影响，并与物理浸渍法进行对比。结果表明：DMMP接枝法具有更高的阻燃效率和更好的抗吸水性能。相较于DMMP物理浸渍，由DMMP接枝亚麻纤维所形成的化学键难以被水分子所破坏，吸水30天后，DMMP接枝的复合材料的极限氧指数(LOI)、垂直燃烧性能、放热和烟雾释放相较于吸水前并未发生明显改变，吸水后阻燃性能保持良好。另一方面，接枝法对于吸水后复合材料的拉伸性能的负面影响也低于物理浸渍法。
- 亚麻纤维 /
- 酚醛树脂 /
- 吸水性能 /
- 阻燃性能 /
- 力学性能
Abstract: In recent years, plant fiber reinforced composites have been widely concerned because of their advantages of environmental protection, high specific modulus and low cost. In order to study the water absorption characteristics of flame retardant treated plant fiber reinforced composites, flax fiber reinforced phenolic composites (Flax/Phenolic, FP) were used as the research object. The flame retardant treatment of flax fiber was carried out by grafting dimethyl methylphosphonate (DMMP), and the optimal treatment process was explored. The water absorption of DMMP grafted composites and its influence on the flame retardancy and tensile properties of the composites were studied, compared with the physical impregnation method. The results show that DMMP grafting method has higher flame retardant efficiency and better water absorption resistance. Compared with physical impregnation method, the chemical bond formed by DMMP grafting is difficult to be destroyed by water molecules. After 30 days of water absorption, the limiting oxygen index (LOI), vertical combustion, heat release and smoke release of DMMP grafted composites have not changed significantly compared with those before water absorption, and the flame retardancy of DMMP grafted composites is well maintained after water absorption. On the other hand, the negative effect of grafting on the tensile properties of composites after water absorption is also lower than that of physical impregnation.
- flax fiber /
- phenolic resin /
- water absorption properties /
- flame retardant properties /
- mechanical pro-perties

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图 1 甲基膦酸二甲酯(DMMP)接枝亚麻纤维反应示意图

Figure 1. Schematic diagram of the reaction of dimethyl methylphosphonate (DMMP) grafted flax fiber

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图 2 亚麻纤维与在100℃和5 h工艺条件下DMMP接枝亚麻纤维的红外图谱

Figure 2. Infrared spectra of flax fiber and DMMP grafted flax fiber treated at 100℃ for 5 h

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图 3 不同工艺条件下DMMP接枝处理对亚麻单纤维拉伸性能的影响

Figure 3. Effect of DMMP grafting treatment on tensile properties of single flax fiber under different process conditions

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图 4 DMMP阻燃改性前后复合材料的吸水率曲线

Figure 4. Water absorption of composites before and after DMMP flame retardant modification

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图 5 DMMP阻燃改性复合材料吸水前和吸水30天后热释放率

Figure 5. Heat release rate of DMMP flame retardant modified composites before water absorption and after water absorption for 30 days

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图 6 DMMP阻燃复合材料吸水前后的拉伸性能变化：(a)拉伸强度；(b)拉伸模量

Figure 6. Change in tensile properties of DMMP flame retardant composites before and after water absorption: (a) Tensile strength; (b) Tensile modulus

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图 7 拉伸试样破坏断面：(a) FP；(b) 10wt%DMMP-P-FP；(c) DMMP-G-FP；吸水30天后的FP (d)、10wt%DMMP-P-FP (e)和DMMP-G-FP (f)

Figure 7. Failure section of tensile specimen: (a) FP; (b) 10wt%DMMP-P-FP; (c) DMMP-G-FP; FP (d), 10wt%DMMP-P-FP (e) and DMMP-G-FP (f) after water absorption for 30 days

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表 1 不同试样的铺层与尺寸

Table 1. Layer and dimension of different sample

Test	Number of layer	Dimension/mm³
Vertical combustion	16	305×75×4
LOI	16	80×10×4
Cone calorimeter	16	100×100×4
Tensile	8	250×15×2
Water absorption	20	35×35×5
Note: LOI—Limit oxygen index.

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表 2 不同复合材料的描述与简写

Table 2. Description and abbreviations of different samples

Sample	Description
FP	Untreated flax/phenolic
DMMP-G-FP	DMMP-grafted flax/phenolic
5wt%DMMP-P-FP	5wt%DMMP physical impregnation treated flax/phenolic
10wt%DMMP-P-FP	10wt%DMMP physical impregnation treated flax/phenolic

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表 3 DMMP接枝亚麻纤维织物后垂直燃烧碳化长度与磷含量

Table 3. Vertical combustion carbonization length and phosphorus content of DMMP grafted treated flax fiber fabric

Condition	3 h	4 h	5 h
80℃	–	–	–
90℃	–	–	–
100℃	–	–	44.8 mm(0.86%)
110℃	–	41.6 mm(0.92%)	38.7 mm(1.06%)
120℃	46.4 mm(1.17%)	35.6 mm(1.18%)	35.1 mm(1.25%)
Notes: "–" indicates that the specimens cannot extinguish after being moved away from the fire; The values in the parentheses are the phosphorus content on the treated flax fabric.

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表 4 DMMP阻燃改性前后复合材料的24 h吸水率

Table 4. Water absorption of composites before and after DMMP flame retardant modification at 24 h

Sample	24 h water absorption/%
FP	1.46
5wt%DMMP-P-FP	2.73
10wt%DMMP-P-FP	3.38
DMMP-G-FP	1.73

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表 5 阻燃改性前后亚麻纤维增强酚醛复合材料垂直燃烧、LOI和老化液中磷含量(括号中为吸水30天后的垂直燃烧、LOI和老化液中磷含量)

Table 5. Vertical combustion, LOI and phosphorus content in aging solution of flax fiber reinforced phenolic composites before and after flame retardant modification (Vertical combustion, LOI and phosphorus content in the aging solution after 30 days of water absorption are in parentheses)

Sample	Self-extinguishing time/s	Carbonization length/mm	LOI/%	Phosphorus content/wt%
FP	–(–)	–(–)	29.2(28.8)	–(–)
5wt%DMMP-P-FP	–(–)	–(–)	32.6(30.9)	–(0.48)
10wt%DMMP-P-FP	9(18)	19.9(49.7)	39.6(35.6)	–(0.67)
DMMP-G-FP	0(0)	18.7(33.8)	44.3(40.5)	–(0.12)

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表 6 复合材料阻燃改性前后锥形量热测试主要数据

Table 6. Main data of cone calorimetry test before and after flame retardant modification of composites

Sample	TTI/s	PHRR/(kW·m⁻²)	THR/(MJ·m⁻²)	TSP/m²
FP	41±2.2	602.36±5.1	161.33±6.3	7.43±0.2
5wt%DMMP-P-FP	53±1.9	306.47±21.4	90.12±15.9	4.12±0.4
10wt%DMMP-P-FP	56±0.7	296.90±31.2	86.54±15.6	3.73±0.7
DMMP-G-FP	57±0.7	325.74±41.7	88.65±2.6	3.25±0.2
5wt%DMMP-P-FP(In water)	46±0.3	593.78±23.8	150.36±14.7	7.03±1.4
10wt%DMMP-P-FP (In water)	51±3.4	560.64±15.5	140.70±6.7	6.87±0.9
DMMP-G-FP (In water)	53±1.7	333.71±30.6	93.61±3.7	3.62±0.3
Notes: TTI—Time to ignition; PHRR—Peak heat release rate; THR—Total heat release; TSP—Total smoke production.

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