碳纤维增强水泥基复合材料界面优化设计研究进展

李子琪; 裴纯; 朱继华

碳纤维增强水泥基复合材料界面优化设计研究进展

深圳大学, 土木与交通工程学院, 深圳518000

基金项目: 国家自然科学基金(52108231)；广东省重点领域研究开发项目(2019B111107002); 深圳市科技创新项目(20220810140230001、20220810160453001)

详细信息

通讯作者:
朱继华，博士，教授，博士生导师，研究方向为碳纤维材料功能化应用等　E-mail: zhujh@szu.edu.cn

中图分类号: TB33
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- 被引次数: 0
出版历程
- 收稿日期: 2024-01-02
- 修回日期: 2024-01-31
- 录用日期: 2024-02-28
- 网络出版日期: 2024-04-11

Current status of interface modification of carbon fiber cement-based composite materials

Shenzhen University, College of Civil and Transportation Engineering, Shenzhen 518000, China

Funds: The National Natural Science Foundation of China [NO.52108231]; Key-Area Research and Development Program of Guangdong Province [NO. 2019B111107002]; The Shenzhen Science and Technology Innovation Program [NO.20220810140230001, 20220810160453001].

摘要

摘要: 碳纤维增强水泥基复合材料(Carbon fiber reinforced cement composite，CFRCC)以其高强度重量比、耐腐蚀性和耐久性而通常用于建筑、基础设施和土木工程等领域。对CFRCC而言，界面是联系基体与增强相的桥梁，界面性能、结构直接关系到复合材料粘结强度，从而直接影响到复合材料的各项宏观性能。然而，碳纤维的疏水性以及其与水性悬浮液之间不充分的结合行为，限制了碳纤维在水泥和其他矿物建筑材料中的应用。为了解决这一问题，学者们研究了物理和化学改性方法，以加强从矿物基质到碳纤维的负载转移。本文介绍了碳纤维、CFRCC及CFRCC界面的性能及存在的问题。总结了近些年国内外学者对CFRCC及其界面改性方法，例如氧化、电泳沉积、等离子体和接枝处理等表面改性方法，并讨论了相关机制分析。还介绍了研究碳纤维本身的特性以及其与水泥基质的结合行为的表征方法。
- 碳纤维 /
- 碳纤维复合材料 /
- 水泥基复合材料 /
- 表面改性 /
- 界面改性 /
- 界面性能
Abstract: Carbon fiber reinforced cement composite (CFRCC) is widely used in the fields of construction, infrastructure, and civil engineering due to its high strength-to-weight ratio, corrosion resistance, and durability. In the context of CFRCC, the interface plays a crucial role as it acts as a bridge connecting the matrix and the reinforcing phase. The performance and structure of the interface directly impact the bond strength of the composite material, thereby influencing its overall macroscopic properties. However, the inherent hydrophobic nature of carbon fibers and their inadequate bonding with aqueous suspensions limit their application in cement and other mineral building materials. To address this issue, researchers have explored physical and chemical modification methods to enhance the transfer of load from the mineral matrix to the carbon fibers. This paper provides an overview of the properties of carbon fibers, CFRCC, and CFRCC interfaces, while also summarizing recent studies by domestic and foreign scholars on CFRCC and its interface modification methods, such as oxidation, electrophoretic deposition, plasma, and grafting treatments, along with discussions on relevant mechanistic analyses. Additionally, it presents characterization methods for studying the properties of carbon fibers themselves and their bonding behavior with cementitious matrices.
- Carbon fiber /
- Carbon fiber composite materials /
- Cement based composite materials /
- Surface modification /
- Interface modification /
- Interface performance

HTML全文

图 1 拉伸破坏机制：(a)连接平行于纤维轴的两个晶粒的取向错误的晶粒; (b)平行于纤维轴施加的拉伸应力导致基面在La方向上断裂，裂纹沿着La和Lc发展; (c)应力的进一步施加导致取向不良的微晶完全失效^[56]

Figure 1. Mechanism of tensile failure: (a) Misoriented crystallite linking two crystallites parallel to fibre axis. (b) Tensile stress exerted parallel to fibre axis causes basal plane rupture in direction La , crack develops along La and Lc. (c) Further exertion of stress causes complete failure of misoriented crytallite.^[56]

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图 2 碳纤维增强水泥基复合材料(CFRCC)的力学性能: ((a) CFRCC弯曲强度与碳纤维质量分数之间的关系^[65]；(b) CFRCC抗压强度与碳纤维质量分数之间的关系^[65]; (c)碳纤维对大理石灰和底灰混合料固化28天和56天抗硫酸盐性能的影响^[66])

Figure 2. Mechanical properties of carbon fiber reinforced cement composite (CFRCC): ((a) The relationship between CFRCC flexural strength and carbon fiber mass fraction^[65]; (b) The relationship between CFRCC compressive strength and carbon fiber mass fraction^[65]; (c)Effect of carbon fiber on sulfate resistance for marble dust and bottom ash mixture groups at 28 and 56 days of curing^[66])

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图 3 CFRCC的功能性: ((a)碳纤维混凝土的电阻率随碳纤维长度和含量的变化^[65]; (b)水泥基传感器中理论传导路径的示意图^[3])

Figure 3. Functionality of CFRCC: ((a)The electrical resistivity of CFRCC varies with carbon fiber length and content^[65]; (b)Schematic presentation of theoretical conduction pathways in a cement-based sensor^[3])

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图 4 纤维-基体界面的失效模式: (a)胶结基体中的失效^[80](b)纤维失效^[80] (c)脱粘失效^[81] (d)纤维-基体之间的界面间隙^[34]

Figure 4. Failure modes of fiber–matrix interface: (a) failure in cementitious matrix^[80] (b) failure in fibers^[80]；(c) debonding failure^[81]; (d) interfacial gap between the CF and cement matrix^[34]

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图 5 (a) 臭氧改性聚乙烯纤维示意图 ^[86]；(b)等离子体氧化碳纤维的成键原理^[87]；(c)涂层法改性碳纤维原理示意^[93]；(d)电化学沉积法改性碳纤维装置示意^[33]；(e)接枝法改性碳纤维原理示意^[81]；(f)浸渍碳纤维装置示意^[103]

Figure 5. (a) Ozone modified polyethylene fiber ^[86]; (b) The bonding principle of plasma oxidation of CF ^[87]; (c) Schematic diagram of the principle of coating method modified CF^[93]; (d) Electrochemical deposition method modified CF device ^[33]; (e) Schematic diagram of grafting method for modifying CF^[81];(f) Impregnation CF device ^[103]

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图 6 化学元素表征方法 ((a)XPS^[81] (b)XRD^[114] (c) FTIR ^[81] (d)Raman ^[119] (e)EDX^[33] (f)TGA^[33])

Figure 6. Characterization method of chemical elements ((a)XPS^[81] (b)XRD^[114] (c) FTIR^[81] (d)Raman^[119] (e)EDX^[33] (f)TGA^[33])

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图 7 表面形貌表征方法 ((a)TEM^[124] (b)EBSD^[93] (c)接触角表征^[130] (d)AFM^[87])

Figure 7. surface morphology characterization method ((a)TEM^[124] (b)EBSD^[93] (c) Contact angle characterization^[130] (d)AFM^[87])

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图 8 纳米压痕示意^[136]

Figure 8. Schematic illustration of nanoindentation^[136]

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图 9 单丝纤维拔出试验的样品制备和装置图^[123,90]

Figure 9. Sample preparation and experimental setup of the single fiber pullout test^[123,90]

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表 1 碳纤维表面改性常用方法

Table 1. Common methods for surface modification of carbon fibers

Surface modification of carbon fiber		Principle	Characteristic
Oxidation method	Electrochemical oxidation	The carbon fiber was electrified by electrochemical method, so that its surface was oxidized and functional groups were introduced to increase the surface active sites of the fiber	Increase fiber surface active sites, but the equipment is complex and the cost is high
	Ozonation	Ozone gas oxidizer was used to oxidize the fiber surface to increase the reactive groups on the fiber surface	Oxidation time is short, reaction conditions are mild and easy to control, but ozone has certain toxicity
	Plasma oxidation	Oxygen dissociates into oxygen atoms or ions to produce oxygen-containing free radicals, which etch the surface of the fiber and generate oxygen-containing functional groups at the fiber defects	It is easy to expand, eco-friendly and efficient, but the equipment is complex and the cost is high
Coating method		Coating on carbon fiber surface by physical or chemical methods	Protect the strength of fiber body, simple process, but limited durability
Deposition method		Under the chemical or electric drive, the groups in the electrolyte will move towards the electrode with opposite charge, so that the desired product is deposited on the surface of carbon fiber	Less damage to the fiber body, functional groups can be deposited, but the preparation efficiency is low, and the process parameters need to be optimized
Grafting method		The introduction of polymer chains or active functional groups such as hydroxyl, carboxyl and amino groups on the surface of carbon fibers through chemical reactions	It has strong controllability and can realize multifunctional modification, but the process is complex and some organic solvents used are not friendly to the environment
Impregnation method		By immersing the fiber in a solution containing mineral components, the mineral components penetrate into the fiber, thereby improving the performance of the fiber	The mineral composition usually used is environment-friendly, low cost and relatively simple process, but it may damage the fiber

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表 2 界面性能表征常用方法

Table 2. Common methods for evaluating interface performance

Characterization Methods	Method Type	Advantages	Advantages
X-ray Photoelectron Spectroscopy (XPS)	Elemental characterization	Provides chemical composition and chemical state information of material surfaces	Requires analysis under vacuum conditions and high surface requirements for samples
X-ray Diffraction (XRD)	Elemental characterization	Provides crystal structure information, beneficial for the analysis of crystalline materials	Unable to provide material chemical composition information, weak in analyzing amorphous materials
Transform Infrared Spectroscopy (FTIR) Elemental characterization	Elemental characterization	Provides molecular structure and chemical bond information of materials, suitable for organic and polymer analysis	Weak in analyzing inorganic crystalline materials Raman
Raman Spectroscopy (Raman)	Elemental characterization	Provides molecular structure and crystal structure information of materials, suitable for non-destructive analysis	Weak signal intensity, weak in surface analysis of materials
Energy Dispersive X-ray Spectroscopy (EDX)	Elemental characterization	Provides material element composition and distribution information, suitable for micro-area analysis	Relatively low resolution, weak in analyzing light elements
Thermogravimetric Analysis (TGA)	Elemental characterization	Provides material thermal stability and thermal decomposition information	Unable to provide material structural information, weak in analyzing non-thermally decomposing materials
Scanning Electron Microscopy (SEM)	Surface morphology characterization	Provides material surface morphology and microstructure information	Unable to provide material chemical composition and crystal structure information
Transmission Electron Microscopy (TEM)	Surface morphology characterization	Provides material microstructure and crystal structure information, particularly suitable for nano-scale material analysis	Requires complex sample preparation and operation techniques, high sample requirements
Electron Backscatter Diffraction (EBSD)	Surface morphology characterization	Provides material crystal structure and grain orientation information	Requires complex sample preparation and operation techniques, high sample requirements
Atomic Force Microscopy (AFM)	Surface morphology characterization	Provides material surface morphology, roughness, and other surface property information	Only provides surface property information, weak in analyzing other properties
Contact Angle Measurement	Polarity characterization	Provides material surface hydrophilicity and hydrophobicity information	Only provides polarity performance information, weak in analyzing other properties
Nanoindentation (NI)	Mechanical testing	Provides material hardness and elastic modulus information	Requires complex sample preparation and operation techniques, high sample requirements
Micro-droplet Detachment Test	Mechanical testing	Mechanical testing Provides material surface adhesion information	Requires complex sample preparation and operation techniques, high sample requirements
Fiber Tensile Testing	Mechanical testing	Provides material tensile mechanical properties	High variability, requires a large number of repeated tests
Fiber Pullout Testing	Mechanical testing	Mechanical testing Provides material interfacial mechanical properties	Requires complex sample preparation and operation techniques, high requirements for samples and testing equipment

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