硅烷改性胶原纤维/聚氯乙烯复合材料的界面相容性及其高弹抗蠕变性研究

雷超; 许维星; 曾运航; 石碧

硅烷改性胶原纤维/聚氯乙烯复合材料的界面相容性及其高弹抗蠕变性研究

雷超¹,
许维星¹,
曾运航^{1, 2, ,},
石碧^{1, 2}

1.
制革清洁技术国家工程实验室(四川大学), 四川成都 610065
2.
四川大学轻工科学与工程学院, 四川成都 610065

基金项目: 国家重点研发计划(基金号：2019YFC1904500)；

详细信息

通讯作者:
曾运航，博士，教授，博士生导师，研究方向为胶原生物质与制革废弃物高值利用技术　E-mail: zengyunhang@scu.edu.cn

中图分类号: TB332
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- HTML全文浏览量: 130
- PDF下载量: 7
- 被引次数: 0
出版历程
- 收稿日期: 2023-08-08
- 修回日期: 2023-09-22
- 录用日期: 2023-09-29
- 网络出版日期: 2023-10-23
- 刊出日期: 2024-06-15

Study on interfacial compatibility and resilient creep resistance of silane-modified collagen fiber/polyvinyl chloride composites

LEI Chao¹,
XU Weixing¹,
ZENG Yunhang^{1, 2
, ,},
SHI Bi^{1, 2}

1.
National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065, China
2.
College of Biomass Science and Engineering, Sichuan University, Chengdu 610065, China

Funds: National Key Research and Development Program of China (No. 2019YFC1904500)

摘要

摘要: 胶原纤维(CF)的三维多层级结构具有对聚氯乙烯(PVC)进行高弹抗蠕变改性的天然优势，但亲水性的CF难以与疏水性的PVC有效相容，这限制了CF对PVC的改性效果。文章用氨基硅烷偶联剂(APTES)制备得到改性CF(M-CF)，并用FESEM、FTIR和DMA等研究了M-CF的结构转变规律，以及M-CF/PVC的结构、蠕变行为和断裂行为。结果表明，APTES能在提高CF疏水性的同时，与PVC分子链形成离子键和共价键，从而显著改善CF与PVC的界面相容性。此外，APTES改性能充分打开M-CF的三维多层级结构，使PVC更好地渗入M-CF相区，并形成更多的作用位点。由此，PVC分子链的运动受到了明显抑制，M-CF/PVC的形变活化能较纯PVC提高了30.7%，蠕变寿命延长至纯PVC的80.5倍和CF/PVC的2.3倍，且可回复形变(11.50%)增至传统改性PVC的1.4倍以上。综上，CF与PVC相容性的提升使M-CF/PVC表现出了理想的高弹抗蠕变性。
- 胶原纤维 /
- 硅烷 /
- 聚氯乙烯 /
- 抗蠕变性 /
- 回弹性
Abstract: The three-dimensional hierarchical structure of collagen fiber (CF) has the natural advantage of resilient creep-resistant modification of polyvinyl chloride (PVC), but the hydrophilic CF is difficult to be compatible with the hydrophobic PVC effectively, which limits the modification efficacy of PVC by CF. Modified CF (M-CF) was prepared with amino-silane coupling agent (APTES). The structural transformation pattern of M-CF, and the structure, creep behavior, and fracture behavior of M-CF/PVC were investigated by FESEM, FTIR, and DMA. The results showed that APTES improved the hydrophobicity of CF and formed ionic and covalent bonds with PVC chains, thereby greatly improving the compatibility between CF and PVC. In addition, APTES modification fully opened the three-dimensional hierarchical structure of M-CF, which allowed PVC to better penetrate into the M-CF phase region and form more blocking sites between PVC and M-CF. As a result, the movement of PVC chains was obviously inhibited, the deformation activation energy of M-CF/PVC was increased by 30.7% compared with that of pure PVC, the creep lifetime of M-CF/PVC was extended to 80.5 times that of pure PVC and 2.3 times that of CF/PVC, and the reversible deformation (11.50%) of M-CF/PVC was increased to more than 1.4 times that of the conventional modified PVC. In summary, the improved compatibility between CF and PVC endowed M-CF/PVC with ideal resilient creep-resistance.
- collagen fiber /
- silane /
- polyvinyl chloride /
- creep resistance /
- resilience

HTML全文

图 1 改性胶原纤维(M-CF)/聚氯乙烯(PVC)的制备过程

Figure 1. Preparation process of modified collagen fiber (M-CF)/ polyvinyl chloride (PVC)

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图 2 CF (a–c)和M-CF (d–f)多层级结构的FESEM图

Figure 2. FESEM images of hierarchical structure of CF (a–c) and M-CF (d–f)

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图 3 CF和M-CF的FTIR光谱(a)、XPS C 1 s能谱(b)、XPS O 1 s能谱(c)、水接触角、表面自由能和外观数码照片(d)

Figure 3. FTIR spectra (a), XPS C 1 s spectra (b), XPS O 1 s spectra (c), water contact angles, surface free energy and digital photos (d) of CF and M-CF

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图 4 不同填料含量的CF/PVC (a–e)和M-CF/PVC (f–j)截面的FESEM图

Figure 4. FESEM images of the sections of CF/PVC (a–e) and M-CF/PVC (f–j) with different filler contents

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图 5 纯PVC、CF/PVC和M-CF/PVC的FTIR光谱(a)、DSC曲线(b)、tanδ(c)和储能模量(d)

Figure 5. FTIR spectra (a), DSC curves (b), tanδ (c) and storage modulus (d) of pure PVC, CF/PVC and M-CF/PVC

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图 6 M-CF与PVC的反应机理示意图：APTES的水解(a)、APTES的缩合(b)、CF表面的反应(c)和M-CF与PVC分子链的反应(d)

Figure 6. Schematic diagram of the reaction mechanism of M-CF and PVC: Hydrolysis of APTES (a), condensation of APTES (b), reaction of CF surface (c), and reaction of M-CF with PVC chains (d)

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图 7 PVC及其复合材料的蠕变-回复曲线(a)、循环蠕变-回复曲线(b)、宾汉模型拟合的蠕变曲线(c)、威布尔分布方程拟合的回复曲线(d)、蠕变柔量主曲线(e)和阿伦尼乌斯方程拟合的活化能曲线(f)

Figure 7. Creep and recovery curves (a), cyclic creep and recovery curves (b), creep ﬁtting curves by Burger’s model (c), recovery ﬁtting curves by Weibull distribution function (d), master curves of creep compliance (e) and activation energy fitting lines by Arrhenius equation (f) of pure PVC and composites

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图 8 CF/PVC(a–c)和M-CF/PVC(d–f)缺口冲击断裂后截面的FESEM图

Figure 8. FESEM images of the notched-impact fractured surfaces of CF/PVC (a–c) and M-CF/PVC (d–f)

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图 9 CF和M-CF对PVC高弹抗蠕变改性机制的示意图

Figure 9. Schematic diagram of mechanism of resilient creep-resistant modification of PVC by CF and M-CF

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表 1 复合材料的原料配比

Table 1. Formulation of composites

Sample	Filler	Filler / PVC (Weight ratio)
Pure PVC		0 / 100
CF₅/PVC	CF	5.26 / 100
CF₁₀/PVC	CF	11.11 / 100
CF₂₀/PVC	CF	25.00 / 100
CF₃₀/PVC	CF	42.86 / 100
CF₄₀/PVC	CF	66.67 / 100
M-CF₅/PVC	M-CF	5.26 / 100
M-CF₁₀/PVC	M-CF	11.11 / 100
M-CF₂₀/PVC	M-CF	25.00 / 100
M-CF₃₀/PVC	M-CF	42.86 / 100
M-CF₄₀/PVC	M-CF	66.67 / 100
M-GF₂₀/PVC	M-GF	25.00 / 100
M-QS₂₀/PVC	M-QS	25.00 / 100

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表 2 PVC及其复合材料的宾汉模型和威布尔分布方程的模拟参数

Table 2. The simulated parameters of the Burger′s model and the Weibull distribution function with pure PVC and composites

Sample	E_M/MPa	E_K/MPa	η_K/(MPa·s)	η_M/s	τ/s	η_r/s	β_r	ε_KV/%	ε_∞/%	ε_SM/%	$ {\text{ε}}_{\text{MAX}}^{\ast } $_/%	ε_R/%
Pure PVC	2.93	0.14	46.04	3361.34	321.66	158.73	0.59	18.65	6.57	6.06	31.28	24.71
CF/PVC	7.14	0.31	159.10	3703.70	511.12	169.10	0.63	9.27	4.96	1.19	15.42	10.46
M-CF/PVC	7.34	0.35	184.25	8908.69	598.94	172.92	0.65	8.98	2.06	2.52	13.56	11.50
M-GF/PVC	12.45	0.40	308.63	10282.78	765.58	265.61	0.88	5.84	1.80	2.34	9.98	8.18
M-QS/PVC	12.81	0.43	348.45	29090.91	804.94	309.69	0.94	5.38	1.75	1.63	8.76	7.01
Notes: E_M, E_K, η_K, and η_M are the modulus of the Maxwell spring, the modulus of the Kelvin spring, the viscosity of the Kelvin dashpot, and the viscosity of the Maxwell dashpot, respectively; τ is the relaxation time; η_r and β_r are the characteristic life factor and the shape parameters, respectively; ε_KV, ε_∞, and ε_SM are the delayed elastic (viscoelastic) deformation, the permanent deformation, and the elastic (instantaneous) deformation, respectively; $ {\text{ε}}_{\text{MAX}}^{\ast } $ is the maximum deformation measured by the creep test; ε_R is the recoverable deformation.

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