基体改性对连续玻纤增强尼龙复合材料性能的影响

张鑫婷; 尹洪峰; 魏英; 汤云; 袁蝴蝶; 任小虎; 杨顺

基体改性对连续玻纤增强尼龙复合材料性能的影响

西安建筑科技大学　材料科学与工程学院, 西安 710055

详细信息

通讯作者:
魏英，博士，讲师，研究方向为聚合物基复合材料　E-mail：weiying@xauat.edu.cn

中图分类号: TB332
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- 文章访问数: 171
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- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2023-09-08
- 修回日期: 2023-10-18
- 录用日期: 2023-11-26
- 网络出版日期: 2024-01-04
- 刊出日期: 2024-07-15

Effect of matrix modification on the properties of continuous glass fiber reinforced nylon composites

College of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China

摘要

摘要: 提升连续玻璃纤维(cGF)增强尼龙6复合材料(cGF/PA6)力学性能的重要途径之一是改善玻纤与尼龙之间的界面结合。本研究将星形支化聚酰胺6(SPA6)应用于cGF/PA6复合材料体系，采用熔融挤出结合热压成型法制备了不同含量SPA6的连续玻璃纤维增强尼龙复合材料(cGF/PA6-SPA6)。通过接触角实验测得SPA6与cGF 具有更相近的极性。DSC检测结果表明PA6与SPA6共混后基体熔融温度相差不大、结晶温度和结晶度有所提高。三点弯曲法测得PA6-SPA6基体的弯曲强度相对于PA6和 SPA6有所降低，但cGF/5wt.%SPA6和cGF/10wt.%SPA6复合材料的弯曲强度相对于cGF/PA6分别提高了4.9%和6.4%。短梁剪切试验测得cGF/5wt.%SPA6和cGF/10wt.%SPA6复合材料的层间剪切强度相对于cGF/PA6分别提高了16.7%和15.6%。悬臂梁摆锤冲击实验测得cGF/PA6和cGF/SPA6复合材料的冲击强度分别是PA6和 SPA6的12倍和26.3倍。结合冲击断口形貌观察，可以推断在cGF/PA6复合材料中加入5wt.%或10wt.%的SPA6可以提高复合材料的弯曲和剪切强度，而对其冲击强度影响不大，且成本较低，具有一定的应用价值。
- 尼龙6 /
- 星形支化尼龙6 /
- 尼龙复合材料 /
- 连续玻璃纤维 /
- 力学性能
Abstract: One of the important ways to improve the mechanical properties of continuous glass fiber (cGF) reinforced nylon 6 composites (cGF/PA6) is to improve the interface interactions between glass fiber and nylon 6. In this study, star-branched polyamide 6 (SPA6) was applied to cGF/PA6 composite system, and continuous glass fiber reinforced nylon composites with different contents of SPA6 (cGF/PA6-SPA6) were prepared by melt extrusion combined with hot pressing. The characterization of Contact Angle indicates that the polarity between SPA6 and cGF is more similar. DSC results show that there is not much difference in the melting temperature among PA6, SPA6 and PA6-SPA6 composite matrix, and both the crystallization temperature and crystallinity of PA6-SPA6 are increased. The flexural strength of PA6-SPA6 matrix is lower than that of PA6 and SPA6 measured by three-point flexural tests. However, compared with cGF/70wt.%PA6, the flexural strength of cGF/5wt.%SPA6 and cGF/10wt.%SPA6 composites increased by 4.9% and 6.4%, respectively, and the shearing strength of cGF/5wt.%SPA6 and cGF/10wt.%SPA6 composites increased by 16.7% and 15.6%, respectively. The impact strength of cGF/PA6 and cGF/SPA6 composites is 12 times and 26.3 times that of PA6 and SPA6, respectively. Combined with the observation of impact fracture morphology, it can be inferred that adding 5wt.% or 10wt.% SPA6 to cGF/PA6 composites can improve the flexural and shearing strength of the composites, while having little influence on the impact strength, and considering its cost-effectiveness, it proves to be of practical value for applications.
- Nylon 6 /
- Star-branched nylon 6 /
- Nylon composites /
- Continuous glass fiber /
- Mechanical property

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图 1 PA6-SPA6基体：(a) XRD曲线；(b) 二次升温熔融曲线；(c) 降温结晶曲线

Figure 1. PA6-SPA6 matrix: (a) XRD curve; (b) Second heating melting curve; (c) Cooling crystallization curve

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图 2 弯曲强度：(a) cGF/PA6-SPA6复合材料；(c) PA6-SPA6基体；层间剪切强度：(b) cGF/PA6-SPA6复合材料；(d) PA6-SPA6基体；(e) cGF/PA6、cGF/5wt.%SPA6复合材料载荷位移曲线

Figure 2. Flexural strength: (a) cGF/PA6-SPA6 composites; (c) PA6-SPA6 matrices; Interlamellar shearing strength: (b) cGF/PA6-SPA6 composites; (d) PA6-SPA6 matrices; (e) Load displacement curves of cGF/PA6 and cGF/5wt.%SPA6 composites

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图 3 PA6-SPA6基体相对黏度和熔融指数

Figure 3. Relative viscosity and melt flow rate of different PA6-SPA6 matrixes

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图 4 (a) 星形支化聚酰胺分子模型；(b) cGF/PA6-SPA6复合材料界面结合示意图

Figure 4. (a) Molecular model of star-branched polyamide; (b) Interface interactions diagram of cGF/PA6-SPA6 composites

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图 5 摆锤冲击强度：(a) cGF/PA6-SPA6复合材料；(b) PA6-SPA6基体

Figure 5. Pendulum impact strength: (a) cGF/PA6-SPA6 composites; (b) PA6-SPA6 matrices

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图 6 PA基复合材料宏观断口形貌：(a) cGF/PA6；(b) cGF/SPA6；PA基复合材料冲击断口形貌SEM图：(c) cGF/PA6；(d) cGF/SPA6；(e) cGF/50wt.%SPA6；(f) cGF/60wt.%SPA6

Figure 6. Macroscopic fracture morphology of PA composites: (a) cGF/PA6; (b) cGF/SPA6; SEM image of impact fracture morphology of PA composites: (c) cGF/PA6; (d) cGF/SPA6; (e) cGF/50wt.%SPA6; (f) cGF/60wt.%SPA6

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表 1 探测液体表面能参数^[33]

Table 1. The surface energy parameters of probe liquids^[33]

Probe liquid	$ {\gamma }_{\mathrm{L}\mathrm{V}} $/(mN·m⁻¹)	$ {\gamma }_{\mathrm{L}\mathrm{V}}^{\mathrm{d}} $/(mN·m⁻¹)	$ {\gamma }_{\mathrm{L}\mathrm{V}}^{\mathrm{p}} $/(mN·m⁻¹)
Water	72.8	21.8	51
Ethylene glycol	48.3	29.3	19
Notes：$ {\gamma }_{\mathrm{L}\mathrm{V}} $,$ {\gamma }_{\mathrm{L}\mathrm{V}}^{\mathrm{d}} $,$ {\gamma }_{\mathrm{L}\mathrm{V}}^{\mathrm{p}} $ are the surface tension, dispersion component, and polarity component of the tested liquid.

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表 2 玻璃纤维(GF)、尼龙6(PA6)及星形支化聚酰胺6(SPA6)固体表面能色散分量、极性分量及总表面能

Table 2. Surface energy dispersion component, polarity component and total surface energy of Glass fiber (GF), Nylon 6 (PA6) and Star branched polyamide 6 (SPA6) solids

	GF	PA6	SPA6
$ {\gamma }_{\mathrm{S}\mathrm{V}}^{\mathrm{d}} $/(mN·m⁻¹)	0.03	1.74	0.85
$ {\gamma }_{\mathrm{S}\mathrm{V}}^{\mathrm{p}} $/(mN·m⁻¹)	90.82	35.05	39.56
$ {\gamma }_{SV} $/(mN·m⁻¹)	90.85	36.79	40.41

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表 3 PA6-SPA6试样名称和组成

Table 3. Name and composition of PA6-SPA6 samples

Sample name	Sample composition/wt.%
Sample name	SPA6	PA6
7.1%SPA6	5	65
14.3%SPA6	10	60
28.6%SPA6	20	50
42.9%SPA6	30	40
57.1%SPA6	40	30
71.4%SPA6	50	20
85.7%SPA6	60	10

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表 4 PA6-SPA6基体XRD参数

Table 4. XRD parameters of PA6-SPA6 matrix

Sample name	α₁(2θ)/(º)	α₂(2θ)/(º)	Crystallinity/%
PA6	20.10	23.88	27.8
7.1%SPA6	20.14	24.04	48.2
14.3%SPA6	20.26	24.00	32
28.6%SPA6	20.20	23.92	47.9
42.9%SPA6	20.21	24.04	30.1
57.1%SPA6	20.32	24.08	31.6
71.4%SPA6	20.12	23.92	37.8
85.7%SPA6	20.46	24.40	36.9
SPA6	20.12	24.00	32.8
Notes：α₁ is the diffraction peak of PA6 (200) and (002) crystal planes, α₂ is the diffraction peak of PA6 (202) crystal plane.

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表 5 DSC二次升温曲线所测PA6-SPA6基体热性能

Table 5. Thermal properties of PA6-SPA6 matrix from DSC second heating curve

Sample	T_m/℃	T_c/℃	∆H_m/(J·g⁻¹)	Crystallinity /%
PA6	217.56	180.14	52.31	27.5
7.1%SPA6	216.4	185.52	65.17	34.3
14.3%SPA6	215.06	184.06	55.61	29.3
28.6%SPA6	217.17	183.72	53.97	28.4
42.9%SPA6	215.04	185.69	60.37	31.8
57.1%SPA6	217.2	185.67	59.73	31.4
71.4%SPA6	215.08	186.75	68.9	36.3
85.7%SPA6	217.19	185.68	60.25	31.7
SPA6	215.85	187.17	70.74	37.2
Notes：T_m, T_c, and ∆H_m are the melting temperature, crystallization temperature, and fusion enthalpy of each sample.

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