聚氨酯-环氧树脂复合材料的力学性能与韧化机制

马衍轩; 付双阳; 王帅飞; 吴睿; 高玉华; 李美玉; 张建; 张鹏; 高嵩

聚氨酯-环氧树脂复合材料的力学性能与韧化机制

马衍轩^{1, 2, ,},
付双阳¹,
王帅飞¹,
吴睿¹,
高玉华¹,
李美玉¹,
张建³,
张鹏^{1, 2},
高嵩^{1, 2}

1.
青岛理工大学　土木工程学院, 青岛 266520
2.
海洋环境混凝土技术教育部工程研究中心, 青岛 266520
3.
青岛青新阳光集团有限公司, 山东青岛 266404

基金项目: 国家自然科学基金项目(52378248)；山东省自然科学基金项目(ZR2022ME121)；中国水利水电科学研究院水利部水工程材料重点实验室(筹)开放研究基金项目(EMF202411)；海洋环境混凝土技术教育部工程研究中心开放课题(TMduracon2022010)；

详细信息

通讯作者:
马衍轩，博士，副教授，硕士生导师，研究方向为防灾减灾材料与技术　E-mail：yxma@qut.edu.cn

中图分类号: TB332
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- HTML全文浏览量: 104
- 被引次数: 0
出版历程
- 收稿日期: 2024-01-12
- 修回日期: 2024-02-28
- 录用日期: 2024-03-02
- 网络出版日期: 2024-04-09

Mechanical properties and toughening mechanism of polyurethane epoxy resin composite materials

MA Yanxuan^{1, 2
, ,},
FU Shuangyang¹,
WANG Shuaifei¹,
WU Rui¹,
GAO Yuhua¹,
LI Meiyu¹,
ZHANG Jian³,
ZHANG Peng^{1, 2},
GAO Song^{1, 2}

1.
School of Civil Engineering, Qingdao University of Technology, Qingdao 266520, China
2.
Engineering Research Center of Concrete Technology under Marine Environment, Ministry of Education, Qingdao 266520, China
3.
Qingdao Qingxin Sunshine Group Co. LTD, Qingdao 266404, China

Funds: This work was financially supported by National Natural Science Foundation of China Project (52378248), Shandong Provincial Natural Science Foundation (ZR2022ME121), the Open Research Fund of Key Laboratory of Engineering Materials of Ministry of Water Resources, China Institute of Water Resources and Hydropower Research (EMF202411), Open Research Fund of Engineering Research Center of Concrete Technology under Marine Environment, Ministry of Education (TMduracon2022010).

摘要

摘要: 环氧树脂材料固化后脆性大、韧性差，表面容易发生老化、龟裂、剥落等问题，难以保护混凝土应对海工环境等复杂的工况。设计、制备了不同体系的聚氨酯/环氧树脂(PU/EP)复合材料，以PU/EP复合材料的拉伸强度、断裂伸长率、冲击韧性作为评价指标进行了正交实验，结合响应面分析法确定了PU/EP复合材料的最佳制备配方为：R值为1、PU掺量为15wt%、制备温度为80℃。研究结果表明：聚氨酯(PU)和EP交联效果良好，PU/EP复合材料的拉伸强度、断裂伸长率、冲击韧性较纯环氧树脂分别提高37.61%、52.21%、47.07%。随着PU掺量的增加，材料中柔性长链段的比例增大，形成二级网络的区域增大，分子间的配位作用以及软连段的增加极大提高了材料的力学性能，并且PU/EP复合材料的硬度和弹性模量有一定程度的降低。
- 环氧树脂 /
- 聚氨酯 /
- 增韧设计 /
- 力学性能 /
- 韧化机制
Abstract: Epoxy resin materials have high brittleness and poor toughness, and are prone to aging, cracking, and peeling on the surface, making it difficult to protect concrete from complex working conditions such as marine environments. Polyurethane/Epoxy resin (PU/EP) composite materials with different systems were designed, and orthogonal experiments were conducted using the tensile strength, fracture elongation, and impact toughness of PU/EP composite materials as evaluation indicators. The optimal preparation formula for PU/EP composite materials was determined through response surface analysis method, with an R value of 1, a PU content of 15wt%, and a preparation temperature of 80℃. The results showed that the crosslinking effect of PU and EP was good, and the tensile strength, fracture elongation, and impact toughness of PU/EP composite materials were improved by 37.61%, 52.21%, and 47.07% compared to pure epoxy resin, respectively. With the increase of PU content, the proportion of flexible long chain segments in the material increases, and the area forming the secondary network increases. The coordination effect between molecules and the increase of soft connecting segments greatly improved the mechanical properties of the material, and the hardness and elastic modulus of PU/EP composite materials are reduced to a certain extent.
- Epoxy resin /
- Polyurethane /
- Toughened design /
- Mechanical /
- Toughening mechanism

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图 1 R值、PU掺量、温度对PU/EP复合材料拉伸强度的响应面

Figure 1. Response surface of R value, PU content and temperature to tensile strength of PU/EP composite.

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图 2 R值、PU掺量、温度对PU/EP复合材料拉伸强度的等高线

Figure 2. Contour lines of R value, PU content and temperature on tensile strength of PU/EP composite.

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图 3 R值、PU掺量、温度对PU/EP复合材料断裂伸长率的响应面

Figure 3. Response surface of R value, PU content and temperature to elongation at break of PU/EP composite

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图 4 R值、PU掺量、温度对PU/EP复合材料断裂伸长率的等高线

Figure 4. Contour lines of R value, PU content, temperature and elongation at break of PU/EP composite.

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图 5 R值、PU掺量、温度对PU/EP复合材料冲击韧性的响应面

Figure 5. Response surface of R value, PU content and temperature to impact toughness of PU/EP composite.

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图 6 R值、PU掺量、温度对PU/EP复合材料冲击韧性的等高线

Figure 6. contour lines of R value, PU content and temperature on impact toughness of PU/EP composite

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图 7 EP、PU和PU/EP复合材料红外图谱

Figure 7. infrared spectra of EP, PU and PU/EP

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图 8 PU/EP复合材料互穿网络示意图

Figure 8. schematic diagram of PU/EP composite interpenetrating network

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图 9 不同掺量下PU/EP复合材料断面的电镜图片：(a) 0wt% (b) 5wt% (c) 10wt% (d) 15wt% (e) 20wt%

Figure 9. electron microscope picture of the cross-section of PU/EP composite with different dosage: (a) 0wt% (b) 5wt% (c) 10wt% (d) 15wt% (e) 20wt%

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图 10 (a) EP、(b) PU/EP冲击断面图片

Figure 10. (a) EP, (b) PU/EP impact cross-section images

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图 11 (a) EP放射区、(b) PU/EP纤维区金相显微镜400倍下形貌特征

Figure 11. morphological characteristics of (a) EP radiation area and (b) PU/EP fiber area under metallographic microscope at 400 x magnification

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图 12 扫描电镜(a)、(b) EP、(c)、(d) PU/EP拉伸断面微观形貌

Figure 12. scanning electron microscopy (a), (b) EP, (c), (d) PU/EP tensile cross-section microstructure

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图 13 纳米压痕示意图: (a)典型负载时间(P-t)、(b)典型荷载位移(P-h)曲线^[29]

Figure 13. schematic diagram of nano-indentation: (a) typical load time(P-t) curve (b) typical load displacement (P-h) curve ^[29]

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图 14 压入和卸载过程及计算参数^[30]

Figure 14. Press-in and Unloading Process and Calculation Parameters^[30]

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图 15 不同PU/EP荷载-深度曲线

Figure 15. Load-depth curves of different PU/EP

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图 16 不同PU掺量样品深度-时间曲线

Figure 16. Depth-time curve of samples with different PU content

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图 17 不同PU掺量样品硬度-深度曲线

Figure 17. Hardness-depth curve of samples with different PU content

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图 18 不同PU掺量样品弹性模量

Figure 18. elastic modulus of samples with different PU content

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表 1 聚氨酯/环氧树脂(PU/EP)复合材料的正交实验设计表

Table 1. Orthogonal test design table of Polyurethane/Epoxy resin (PU/EP) composite

Group number	A Numerical value	B Dosage/%	C Temperature/ ℃
1(A₁B₁C₁)	0.8	5	70
2(A₁B₂C₂)	0.8	10	80
3(A₁B₃C₃)	0.8	15	90
4(A₁B₄C₄)	0.8	20	100
5(A₂B₁C₂)	0.9	5	80
6(A₂B₂C₁)	0.9	10	70
7(A₂B₃C₄)	0.9	15	100
8(A₂B₄C₃)	0.9	20	90
9(A₃B₁C₃)	1.0	5	90
10(A₃B₂C₄)	1.0	10	100
11(A₃B₃C₁)	1.0	15	70
12(A₃B₄C₂)	1.0	20	80
13(A₄B₁C₄)	1.1	5	100
14(A₄B₂C₃)	1.1	10	90
15(A₄B₃C₂)	1.1	15	80
16(A₄B₄C₁)	1.1	20	70

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表 2 PU/EP复合材料测试结果

Table 2. Test results of PU/EP composite

Group number	Tensile strength/MPa	Elongation at break/%	Impact Strength/(J·m⁻²)
1(A₁B₁C₁)	22.12	14.30	20.33
2(A₁B₂C₂)	21.08	18.24	21.01
3(A₁B₃C₃)	24.25	20.15	25.15
4(A₁B₄C₄)	20.65	23.22	27.33
5(A₂B₁C₂)	19.85	14.73	17.54
6(A₂B₂C₁)	22.31	15.21	21.23
7(A₂B₃C₄)	24.67	23.45	25.33
8(A₂B₄C₃)	18.23	26.51	25.55
9(A₃B₁C₃)	23.44	14.45	18.44
10(A₃B₂C₄)	25.15	18.72	23.87
11(A₃B₃C₁)	32.35	25.34	30.40
12(A₃B₄C₂)	21.89	26.42	24.43
13(A₄B₁C₄)	22.84	14.16	16.44
14(A₄B₂C₃)	24.54	15.74	20.45
15(A₄B₃C₂)	29.64	20.14	26.88
16(A₄B₄C₁)	21.89	30.41	23.58

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表 3 PU/EP复合材料实验设计与力学性能

Table 3. Experimental Design and Results of PU/EP composite

Number	R	Dosage/wt%	Temperature/℃	Tensile strength/MPa	Elongation at break/%	Impact Strength/(J·m⁻²)
1	1.0	20	70	21.75	28.04	19.87
2	1.1	15	70	30.50	24.53	27.33
3	1.1	10	80	22.11	14.24	15.53
4	1.1	15	90	31.63	23.88	24.02
5	1.0	20	90	23.53	28.15	18.67
6	0.9	15	70	29.96	25.04	22.43
7	0.9	15	90	28.13	24.32	23.33
8	1.0	15	80	31.14	25.37	28.35
9	1.0	15	80	31.03	25.21	28.87
10	0.9	20	80	22.89	27.42	20.58
11	1.0	15	80	30.76	25.30	29.33
12	1.0	15	80	32.35	26.21	30.40
13	1.0	10	90	20.66	13.21	13.24
14	1.1	20	80	27.23	29.25	20.67
15	0.9	10	80	21.89	12.41	13.24
16	1.0	15	80	30.80	24.87	29.86
17	1.0	10	70	21.61	13.44	12.67

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表 4 回归方差分析

Table 4. Analysis of Regression Variance

Source	Sum of squares	Freedom	Mean square	F	P
Model	306.82	9	34.09	73.59	＜0.0001
A	9.25	1	9.25	19.96	0.0029
B	10.42	1	10.42	22.49	0.0021
C	0.002113	1	0.002113	0.00456	0.9480
AB	4.24	1	4.24	9.16	0.0192
AC	2.19	1	2.19	4.73	0.0662
BC	1.86	1	1.86	4.02	0.0849
A²	0.24	1	0.24	0.53	0.4915
B²	264.56	1	264.56	571.10	＜0.0001
C²	8.27	1	8.27	17.86	0.0039
Residual	3.24	7	0.46
Misfit term	1.54	3	0.51	1.20	0.4169
Error	1.71	4	0.43
Sum	310.06	16
Notes: F-value is the statistic of the F-test; P-value is a constant criterion in hypothesis testing

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表 5 回归方差分析(断裂伸长率)

Table 5. Regression analysis of variance (elongation at break)

Source	Sum of squares	Freedom	Mean square	F	P
Model	521.39	9	57.93	104.94	<0.0001
A	0.9180	1	0.9180	1.66	0.2382
B	443.42	1	443.42	803.24	<0.0001
C	0.2775	1	0.2775	0.5027	0.5012
AB	0.00001	1	0.00001	0.00001	1.0000
AC	0.0012	1	0.0012	0.0022	0.9637
BC	0.0289	1	0.0289	0.0524	0.8256
A²	0.7243	1	0.7243	1.31	0.2897
B²	72.42	1	72.42	131.18	<0.0001
C²	1.20	1	1.20	2.18	0.1832
Residual	3.86	7	0.5520
Incoherent orientation	2.88	3	0.9602	3.90	0.1106
Error	0.9837	4	0.2459
Total	525.26	16

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表 6 回归方差分析(冲击韧性)

Table 6. Regression analysis of variance (impact toughness)

Source	Sum of squares	Freedom	Mean square	F	P
Model	604.41	9	67.16	109.85	＜0.0001
A	7.94	1	7.94	12.99	0.0087
B	78.81	1	78.81	128.91	＜0.0001
C	1.16	1	1.16	1.89	0.2116
AB	1.21	1	1.21	1.98	0.2023
AC	4.43	1	4.43	7.25	0.0310
BC	0.7832	1	0.7832	1.28	0.2950
A²	14.35	1	14.35	23.47	0.0019
B²	421.98	1	421.98	690.23	＜0.0001
C²	44.16	1	44.16	72.23	＜0.0001
Residual	4.28	7	0.6114
Incoherent orientation	1.69	3	0.5623	0.8675	0.5276
Error	2.59	4	0.6482
Total	608.69	16

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[1]	MA Y, ZHANG Y, LIU J, et al. Self-Healing Epoxy Coating Modified by Double-Walled Microcapsules Based Polyurea for Metallic Protection[J]. Key Engineering Materials, 2019, 821: 313-320. doi: 10.4028/www.scientific.net/KEM.821.313
[2]	马衍轩, 宋晓辉, 于霞, 等. 海工钢筋环氧涂层的多尺度结构设计与防护性能调控研究进展[J/OL][J]. 材料导报, 2023, (24): 1-26. MA Y, SONG X, YU X, et al. Research progress on multi-scale structural design and protective performance control of epoxy coatings for marine steel reinforcement[J]. Material Guide, 2023, (24): 1-26(in Chinese).
[3]	袁玉环, 左进霞, 彭聪, 等. 聚氨酯/纳米SiO₂改性碳纤维增强环氧树脂复合材料界面性能[J]. 复合材料学报, 2023, 40(11): 6073-6086. YUAN Y, ZUO J, PENG C, et al. Polyurethane/Nano SiO_ Interface properties of modified carbon fiber reinforced epoxy resin composite materials[J]. Journal of Composite Materials, 2023, 40(11): 6073-6086(in Chinese).
[4]	MAROUF B T, MAI Y W, BAGHERI R, et al. Toughening of Epoxy Nanocomposites: Nano and Hybrid Effects[J]. Polymer Reviews, 2016, 56(1): 70-112. doi: 10.1080/15583724.2015.1086368
[5]	NEVES R M, ORNAGHI H L, ZATTERA A J, et al. Toughening Epoxy Resin with Liquid Rubber and Its Hybrid Composites: A Systematic Review[J]. Journal of Polymer Research, 2022, 29(8): 340. doi: 10.1007/s10965-022-03195-z
[6]	JAYAN J S, SARITHA A, JOSEPH K. Innovative Materials of This Era for Toughening the Epoxy Matrix: A Review[J]. Polymer Composites, 2018, 39(S4): E1959-E1986.
[7]	MERZ E H, CLAVER G C, BAER M. Studies on Heterogeneous Polymeric Systems[J]. Journal of Polymer Science, 1956, 22(101): 325-341. doi: 10.1002/pol.1956.1202210114
[8]	AMOS J L. The SPE International Award Address—1973 the Development of Impact Polystyrene–A Review[J]. Polymer Engineering & Science, 1974, 14(1): 1-11.
[9]	李瑜, 邓金飞, 孙昭宜, 等. 端氨基聚硫橡胶增韧改性环氧树脂[J]. 高分子材料科学与工程, 2019, 35(6): 100-104. LI Y, DENG J, SUN Z, et al. Modified epoxy resin toughened by amino terminated polysulfide rubber[J]. Polymer Material Science and Engineering, 2019, 35(6): 100-104(in Chinese).
[10]	WANG J F, ZHANG X H, JIANG L, et al. Advances in Toughened Polymer Materials by Structured Rubber Particles[J]. Progress in Polymer Science, 2019, 98: 101160. doi: 10.1016/j.progpolymsci.2019.101160
[11]	GAO Y L, SUN L Y, CHEN P C, et al. A stretch hardening self-assembly strategy inspired by natural rubber for degradable, recyclable and self-repairing polyurethane elastomers, Polymer Degradation and Stability, Volume 215, 2023, 110441, ISSN 0141-3910.
[12]	D M, TISS L, D J, et al. Protective films on complex substrates of thermoplastic and cellular elastomers: Prospective applications to rubber, nylon and cork, Surface and Coatings Technology, Volume 442, 2022, 128405, ISSN 0257-8972.
[13]	姚佳伟, 冯瑞瑄, 牛一凡, 等. 纳米碳材料/热塑性树脂层间增韧热固性树脂基复合材料研究进展[J]. 复合材料学报, 2022, 39(2): 528-543. YAO J, FENG R, NIU Y, et al. Research progress in nanocarbon materials/thermoplastic resin interlayer toughening thermosetting resin based composites[J]. Journal of Composite Materials, 2022, 39(2): 528-543 (in Chinese).
[14]	李泽宇, 邓夏玲, 韩威, 等. 高韧性和自修复的壳聚糖-聚丙烯酸-MXene导电水凝胶及其压力传感性能[J/OL]. 复合材料学报, 1-10 2023-12-13]. LI Z, DENG X, HANG W, et al. Chitosan polyacrylic acid MXene conductive hydrogel with high toughness and self-healing and its pressure sensing properties[J/OL]. Journal of Composite Materials, 2022, 39(02): 528-543 (in Chinese).
[15]	P P, PUGLIA D, AL M, et al. Elastomer/thermoplastic Modified Epoxy Nanocomposites: The Hybrid Effect of 'Micro' and 'Nano' Scale[J]. Materials Science & Engineering R-Reports, 2017, 116: 1-29.
[16]	CHEN D, LI J, YUAN Y, et al. A new strategy to improve the toughness of epoxy thermosets by introducing the thermoplastic epoxy, Polymer, Volume 240, 2022, 124518, ISSN 0032-3861.
[17]	翟乐, 吉海峰, 姚艳梅, 等. 利用聚丙烯酸正丁酯@聚甲基丙烯酸甲酯核/壳结构聚合物增韧氰酸酯树脂[J]. 材料导报, 2019, 33(4): 705-708. ZHAI Y, JI H, YAO Y, et al. Toughening of cyanate ester resin using poly (n-butyl acrylate) @ poly (methyl methacrylate) core/shell structure polymer[J]. Material Guide, 2019, 33(4): 705-708(in Chinese).
[18]	SHENG W, MEHMET C, Kali B, et al. The effect of hygrothermal ageing on the delamination of Carbon/epoxy laminates with Core-shell rubber nanoparticle and Micro-fibre thermoplastic veil toughening, Composites Part A: Applied Science and Manufacturing, Volume 171, 2023, 107576, ISSN 1359-835X.
[19]	MOUSAVI S R, ESTAJI S, JAVIDI M R, et al. Toughening of Epoxy Resin Systems Using Core-Shell Rubber Particles: A Literature Review[J]. Journal of Materials Science, 2021: 1-23.
[20]	JAWAD M, AQSA A, MUHAMMAD H, et al. Electrophoretic deposition of moringa loaded chitosan coatings on Mg: A study on antibacterial properties and degradation kinetics, Materials Letters, Volume 354, 2024, 135430, ISSN 0167-577X.
[21]	CHEN S F, Xu Z J, ZHANG D H. Synthesis and Application of Epoxy-ended Hyperbranched Polymers[J]. Chemical Engineering Journal, 2018, 343: 283-302. doi: 10.1016/j.cej.2018.03.014
[22]	SANTIAGO D, SERRA A. Enhancement of Epoxy Thermosets with Hyperbranched and Multiarm Star Polymers: A Review[J]. Polymers, 2022, 14(11): 2228. doi: 10.3390/polym14112228
[23]	张雅, 柴春鹏, 罗运军, 等. 超支化聚酯基二茂铁/环氧树脂复合材料的制备及性能[J]. 复合材料学报, 2013, 30(6): 48-53. ZHANG Y, CAHI C, LUO Y, et al. Preparation and properties of hyperbranched polyester based ferrocene/epoxy resin composite materials[J]. Journal of Composite Materials, 2013, 30(6): 48-53(in Chinese).
[24]	K D, M D. Network structure formation during crosslinking of organic coating systems, Progress in Polymer Science, Volume 25, Issue 9, 2000, Pages 1215-1260, ISSN 0079-6700.
[25]	张代军, 包建文, 钟翔屿, 等. 聚醚砜超细纤维无纺布层间增韧碳纤维/环氧树脂复合材料制备与表征[J]. 复合材料学报, 2022, 39(8): 3767-3775. ZHANG D, BAO J, ZHONG X, et al. Preparation and characterization of polyethersulfone ultrafine fiber non-woven fabric interlayer toughened carbon fiber/epoxy resin composite materials[J]. Journal of Composite Materials, 2022, 39(8): 3767-3775(in Chinese).
[26]	FAROOQ U, TEUWEN J, DRANSFELD C. Toughening of Epoxy Systems with Interpenetrating Polymer Network (IPN): A Review[J]. Polymers, 2020, 12(9): 1908. doi: 10.3390/polym12091908
[27]	LIGON-AUER S C, SCH M, GOR C, et al. Toughening of Photo-Curable Polymer Networks: A Review[J]. Polymer Chemistry, 2016, 7(2): 257-286. doi: 10.1039/C5PY01631B
[28]	CAI M, LIN Q, LI W, et al. Phen@TiO2 modified epoxy resin/polyacrylate IPN composite coating towards wear/corrosion resistance and intelligent self-repairing/diagnosis, Progress in Organic Coatings, Volume 173, 2022, 107207, ISSN 0300-9440.
[29]	WANG S. , ZHAO H. Low Temperature Nanoindentation: Development and applications[J]. Micromachines, 2020, 11(4): 407. doi: 10.3390/mi11040407
[30]	PHARR G M, OLIVER W C, BROTZEN F R. On the Generality of the Relationship Among Contact Stiffness, Contact Area, and Elastic Modulus During Indentation[J]. Journal of Materials Research, 1992, 7(3): 613-617. doi: 10.1557/JMR.1992.0613