磷钨酸插层ZnAl层状双金属氢氧化物协同膨胀阻燃剂对环氧-聚酰胺树脂的阻燃作用

汤连东; 吴袁泊; 袁利萍; 胡云楚; 刘月姣; 范友华

doi:10.13801/j.cnki.fhclxb.20200512.001

磷钨酸插层ZnAl层状双金属氢氧化物协同膨胀阻燃剂对环氧-聚酰胺树脂的阻燃作用

doi: 10.13801/j.cnki.fhclxb.20200512.001

1.
中南林业科技大学　材料科学与工程学院，长沙 410004
2.
中南林业科技大学　理学院，长沙 410004
3.
湖南省林科院，长沙 410004

基金项目: 国家自然科学基金(31670563)；湖南省高校生物质复合材料创新平台基金(18K058)

详细信息

通讯作者:
袁利萍，博士，副教授，硕士生导师，研究方向为材料阻燃　E-mail：tiansiyuan@126.com

中图分类号: TB332；TQ323.5
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出版历程
- 收稿日期: 2019-11-06
- 录用日期: 2020-04-22
- 网络出版日期: 2020-05-12
- 刊出日期: 2020-09-15

Flame retardant effect of phosphotungstic acid intercalated ZnAl layered double hydroxides and intumescent flame retardant on epoxy-polyamide resin

TANG Liandong^1
,,
WU Yuanbo^2
,,
YUAN Liping^{1
, ,},
HU Yunchu^1
,,
LIU Yuejiao^1
,,
FAN Youhua^3
,

1.
College of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha 410004, China
2.
School of Science, Central South University of Forestry and Technology, Changsha 410004, China
3.
Hunan Academy of Forestry, Changsha 410004, China

摘要

摘要: 采用[PW₁₂O₄₀]³⁻离子柱撑插层共沉淀法合成的ZnAl硝酸根(NO₃-ZnAl)层状双金属氢氧化物(LDHs)，制备了PW₁₂O₄₀-ZnAl LDHs，并利用XRD、FTIR、电感耦合等离子体(ICP)、SEM等进行组成和结构的表征。将NO₃-ZnAl LDHs和PW₁₂O₄₀-ZnAl LDHs分别与含聚磷酸铵、三聚氰胺、季戊四醇的膨胀阻燃剂(IFRs)复合阻燃环氧-聚酰胺树脂(EP-PA)，采用TGA、背温实验和锥形量热实验评价不同ZnAl LDHs与IFRs复合阻燃EP-PA的热及烟气的释放规律。TGA结果表明，PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的最大降解速率最小，残炭率最高，说明PW₁₂O₄₀-ZnAl LDHs提高了IFRs/(EP-PA)复合材料高温下的抗氧化能力。背温实验表明，相同热辐射强度下，PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的背温达到200℃和300℃用时最长，具有最低的背温升温速率，说明PW₁₂O₄₀-ZnAl LDHs使IFRs/(EP-PA)复合材料耐火能力明显增强。从锥形量热实验数据可知，PW₁₂O₄₀-ZnAl-IFRs使PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料具有最低的热释放速率峰值(PHRR)、平均热释放速率(MHRR)、平均有效燃烧热(MEHC)和总热释放量(THR)，其火势增长指数(FGI)仅为IFRs/(EP-PA)复合材料的14.5%，烟释放总量(TSP)比NO₃-ZnAl-IFRs/(EP-PA)复合材料减少了27.6%，比IFRs/(EP-PA)复合材料减少了55.3%。说明PW₁₂O₄₀-ZnAl-IFRs比NO₃-ZnAl-IFRs更能有效地减少EP-PA的热量释放，抑制烟气生成。
- ZnAl层状双金属氢氧化物 /
- 插层改性 /
- 环氧-聚酰胺树脂 /
- 阻燃 /
- 背温速率
Abstract: The PW₁₂O₄₀-ZnAl layered double hydroxides(LDHs) was prepared by using [PW₁₂O₄₀]³⁻ ion pillared intercalation NO₃-ZnAl LDHs. The composition and structure were analyzed by XRD, FTIR, inductively coupled plasma(ICP) and SEM. The flame retardant epoxy-polyamide resin(EP-PA) were prepared by NO₃-ZnAl LDHs or PW₁₂O₄₀-ZnAl LDHs compound with intumescent flame retardants(IFRs) containing ammonium polyphosphate, melamine, pentaerythritol. The heat and smoke release rules of different ZnAl LDHs-IFRs flame retardant EP-PA were evaluated by back temperature experiment and cone calorimetry experiment. TGA result shows that the maximum degradation rate of PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composite is the lowest, and the carbon residue rate is the highest, which indicate that PW₁₂O₄₀-ZnAl LDHs improve the oxidation resistance of PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composite at high temperature. The back temperature experiment results show that under the same heat radiation intensity, the back temperature of PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composite reaches to 200℃ and 300℃ with the longest time and the lowest rate of back temperature rise. The results show that PW₁₂O₄₀-ZnAl LDHs can obviously enhance the fire resistance of EP-PA. From cone calorimetry experimental data, it can be seen that PW₁₂O₄₀-ZnAl-IFRs makes PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composite have the lowest peak of heat release rate(PHRR), mean heat release rate(MHRR), mean effective heat of combustion(MEHC) and total heat release(THR). Its fire growth index (FGI) is only 14.5% of IFRs/(EP-PA) composite, and the total smoke production (TSP) is 27.6% lower than NO₃-ZnAl-IFRs/(EP-PA) composite and 55.3% lower than IFRs/(EP-PA) composite. The results suggest that PW₁₂O₄₀-ZnAl-IFRs is more effective than NO₃-ZnAl-IFRs in reducing the heat release and inhibiting the generation of flue gas.
- ZnAl layered double hydroxides /
- intercalation modification /
- epoxy-polyamide resin /
- flame retardant /
- back temperature rate

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图 1 LDHs-IFRs/(EP-PA)复合材料背温实验示意图

Figure 1. Schematic diagram of back temperature experiment for LDHs-IFRs/(EP-PA) composites

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图 2 NO₃-ZnAl LDHs和PW₁₂O₄₀-ZnAl LDHs的XRD图谱

Figure 2. XRD patterns of NO₃-ZnAl LDHs and PW₁₂O₄₀-ZnAl LDHs

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图 3 H₃PW₁₂O₄₀·xH₂O、NO₃-ZnAl LDHs和PW₁₂O₄₀-ZnAl LDHs的FTIR图谱

Figure 3. FTIR spectra of H₃PW₁₂O₄₀·xH₂O, NO₃-ZnAl LDHsand PW₁₂O₄₀-ZnAl LDHs

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图 4 NO₃-ZnAl LDHs(a)和PW₁₂O₄₀- ZnAl LDHs(b)的SEM图像

Figure 4. SEM images of NO₃-ZnAl LDHs(a) and PW₁₂O₄₀- ZnAl LDHs(b)

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图 5 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的TG曲线

Figure 5. TG curves of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites

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图 6 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的背温升温曲线

Figure 6. Experimental curves of back temperature of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites

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图 7 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的热释放速率(HRR)曲线

Figure 7. Heat release rate(HRR) curves of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites

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图 8 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的总热释放量(THR)曲线

Figure 8. Total heat release (THR) curves of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites

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图 9 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的烟释放总量(TSP)曲线

Figure 9. Total smoke produce(TSP) curves of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites

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图 10 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料锥形量热实验残炭的数码照片

Figure 10. Digital photographs of residual carbon of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites after cone calorimeter experiment

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图 11 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料锥形量热实验残余物的SEM图像

Figure 11. SEM images of residue of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites after cone calorimeter experiment

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表 1 层状双金属氢氧化物-膨胀阻燃剂/(环氧-聚酰胺树脂)(LDHs-IFRs/(EP-PA))复合材料配比

Table 1. Proportion of layered double hydroxides- intumescent flame retardants/(epoxy-polyamide resin) (LDHs-IFRs/(EP-PA)) composites

Sample	EP/g	PA/g	IFRs/g	LDHs/g
Sample	EP/g	PA/g	IFRs/g	NO₃-ZnAl	PW₁₂O₄₀-ZnAl
IFRs/(EP-PA)	10	10	5.00	0	0
NO₃-ZnAl-IFRs/(EP-PA)	10	10	3.75	1.25	0
PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)	10	10	3.75	0	1.25

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表 2 NO₃-ZnAl LDHs 和 PW₁₂O₄₀-ZnAl LDHs的XRD衍射参数

Table 2. XRD parameters of NO₃-ZnAl LDHs and PW₁₂O₄₀-ZnAl LDHs

Crystal face	NO₃-ZnAl LDHs		PW₁₂O₄₀-ZnAl LDHs
Crystal face	2θ/(°)	d/nm	2θ/(°)	d/nm
(003)	9.94	0.8888	7.96	1.1090
(006)	19.92	0.4452	18.24	0.4858
(009)	33.76	0.2651	33.36	0.2682
(110)	60.30	0.1533	60.40	0.1531
a/nm	0.3066		0.3061
c/nm	2.6660		3.3270
Notes：d—Interplanar distance; θ—Angle of deviation; a=2d₍₁₁₀₎; c=3d₍₀₀₃₎.

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表 3 NO₃-ZnAl LDHs和PW₁₂O₄₀-ZnAl LDHs的元素分析结果

Table 3. Elemental analysis results of NO₃-ZnAl LDHs and PW₁₂O₄₀-ZnAl LDHs

Sample	Zn/wt%	Al/wt%	W/wt%	Chemical formula
NO₃-ZnAl LDHs	5.57	42.80	–	${\rm{Z}}{{\rm{n}}_{{\rm{0}}{\rm{.76}}}}{\rm{A}}{{\rm{l}}_{{\rm{0}}{\rm{.24}}}}{{\rm{(OH)}}_{\rm{2}}}{{\rm{(N}}{{\rm{O}}_{\rm{3}}}{\rm{)}}_{{\rm{0}}{\rm{.24}}}} \cdot {\rm{0}}{\rm{.59}}{{\rm{H}}_{\rm{2}}}{\rm{O}}$
PW₁₂O₄₀-ZnAl LDHs	3.47	22.50	37.13	${\rm{Z}}{{\rm{n}}_{{\rm{0}}{\rm{.73}}}}{\rm{A}}{{\rm{l}}_{{\rm{0}}{\rm{.27}}}}{{\rm{(OH)}}_{\rm{2}}}{{\rm{(P}}{{\rm{W}}_{{\rm{12}}}}{{\rm{O}}_{{\rm{40}}}}{\rm{)}}_{{\rm{0}}{\rm{.037}}}}{{\rm{(N}}{{\rm{O}}_{\rm{3}}}{\rm{)}}_{{\rm{0}}{\rm{.16}}}}$ $ \cdot {\rm{0}}{\rm{.58}}{{\rm{H}}_{\rm{2}}}{\rm{O}}$

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表 4 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的TG数据

Table 4. TG data of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites

Sample	T_5%/℃	T_50%/℃	T_70%/℃	R_max1/(%·℃⁻¹)	Residue at 700℃/%
IFRs/(EP-PA)	104.9	329.1	410.2	0.71	3.47
NO₃-ZnAl-IFRs/(EP-PA)	86.1	328.3	415.7	0.69	4.42
PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)	95.1	330.1	426.2	0.66	6.05
Notes: T_5%, T_50%, T_70%—Temperature corresponding to 5%, 50% and 70% of degradation mass, respectively; R_max1—Maximum degradation rate.

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表 5 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的背温实验结果

Table 5. Back temperature test results of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites

Sample	Fire resistance time/s		V_200℃/(℃·s⁻¹)	V_300℃/(℃·s⁻¹)
Sample	t_200℃	t_300℃	V_200℃/(℃·s⁻¹)	V_300℃/(℃·s⁻¹)
IFRs/(EP-PA)	459.5	942.5	0.44	0.33
NO₃-ZnAl-IFRs/(EP-PA)	618.0	916.0	0.32	0.32
PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)	764.0	1 526.0	0.26	0.20
Notes: V_200℃—Back temperature rising rate at 200℃;V_300℃—Back temperature rising rate at 300℃.

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表 6 IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的锥形量热实验数据

Table 6. Cone calorimetry test data of IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA) composites

Sample	TTI/$ \mathrm{s} $	PHRR/ (kW·m⁻²)	MHRR/ (kW·m⁻²)	THR/ (MJ·m⁻²)	MEHC/ (MJ·kg⁻¹)	TSP/ (m²·m⁻²)	FGI/ (kW·(s·m²)⁻¹)
IFRs/(EP-PA)	154.0	388.3	140.8	60.6	20.3	4.7	2.35
NO₃-ZnAl-IFRs/(EP-PA)	227.0	317.5	118.5	39.4	20.2	2.9	1.48
PW₁₂O₄₀-ZnAl- IFRs/(EP-PA)	281.0	136.3	62.3	28.2	14.5	2.1	0.34
Notes: TTI—Ignition time; PHRR—Peak of heat release rate; MHRR—Mean heat release rate; THR—Total heat release; MEHC—Mean effective heat of combustion; TSP—Total smoke produce; FGI—Fire growth index.

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表 7 EP-PA、IFRs/(EP-PA)、NO₃-ZnAl-IFRs/(EP-PA)和PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)复合材料的力学性能

Table 7. Mechanical properties of EP-PA, IFRs/(EP-PA), NO₃-ZnAl-IFRs/(EP-PA) and PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)composites

Sample	Tensile strength/MPa	Tear strength/(N·mm⁻¹)	Elongation at break/%
EP-PA	11.47	42.83	10.87
IFRs/(EP-PA)	8.12	31.40	16.93
NO₃-ZnAl-IFRs/(EP-PA)	7.86	30.23	19.60
PW₁₂O₄₀-ZnAl-IFRs/(EP-PA)	8.03	30.62	19.39

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