WO2022252260A1 - 一种自润滑涂层及其制备方法与应用 - Google Patents

一种自润滑涂层及其制备方法与应用 Download PDF

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WO2022252260A1
WO2022252260A1 PCT/CN2021/098976 CN2021098976W WO2022252260A1 WO 2022252260 A1 WO2022252260 A1 WO 2022252260A1 CN 2021098976 W CN2021098976 W CN 2021098976W WO 2022252260 A1 WO2022252260 A1 WO 2022252260A1
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carbon fiber
fiber cotton
self
molybdenum disulfide
preparation
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PCT/CN2021/098976
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English (en)
French (fr)
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张伟
马洪才
张梅
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德州学院
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/53—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with hydrogen sulfide or its salts; with polysulfides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

Definitions

  • the invention belongs to the technical field of self-lubricating coatings, in particular to a self-lubricating coating and its preparation method and application.
  • Friction materials are widely used in various transportation vehicles (such as automobiles, trains, airplanes, ships, etc.) and brakes, clutches and friction transmissions of various machinery and equipment.
  • the friction performance of the friction material is used to convert the kinetic energy of the rotation into heat energy and other forms of energy, so that the transmission device is braked.
  • Self-lubricating coating technology refers to the method of coating or plating solid substances on the friction pair interface as a solid lubricating material or solid lubricant to lubricate the friction pair interface to reduce friction or reduce friction.
  • the fibers that can be used for material reinforcement mainly include carbon fiber, ceramic fiber, glass fiber, aramid fiber, etc. At present, in view of the excellent performance of carbon fiber, it is widely used as a reinforcing phase, and molybdenum disulfide, graphite, talcum powder, soft metal, and metal oxide are used as lubricating phases to prepare carbon fiber coatings with self-lubricating functions.
  • Adhesives are often used for bonding between the reinforcing phase and the lubricating phase.
  • the existing adhesives are generally epoxy resin adhesives, polyurethane adhesives, polyvinyl acetate adhesives, etc.
  • the inventors found that the existing The mechanical strength and self-lubricating effect of self-lubricating carbon fiber coatings are relatively limited, and further exploration is needed to obtain coating materials with high mechanical strength and self-lubricating effect.
  • the present invention provides a self-lubricating coating and its preparation method and application.
  • the self-lubricating coating uses carbon fiber cotton as a reinforcing phase, molybdenum disulfide as a lubricating phase, and phenolic acetal as an adhesive , the coating material not only has high mechanical strength, but also can achieve excellent self-lubricating effect, and can be widely used as a braking material in brakes, clutches and friction transmissions of various machinery and equipment.
  • the first aspect of the present invention provides a self-lubricating coating, which uses carbon fiber cotton as the material skeleton, and molybdenum disulfide and phenolic acetal adhesive are filled in the skeleton voids.
  • the mass ratio of carbon fiber cotton, molybdenum disulfide, and phenolic acetal adhesive is (50-55):(0.9-1.1):(9-11).
  • the second aspect of the present invention provides a method for preparing the above-mentioned self-lubricating coating, specifically:
  • Step 1 Measure molybdenum disulfide and phenolic acetal adhesive in a certain proportion and mix them evenly;
  • Step 2 Take an appropriate amount of carbon fiber cotton, and soak the carbon fiber cotton in the adhesive mixed with molybdenum disulfide until it is completely soaked;
  • Step three select a board of appropriate size and place the soaked carbon fiber cotton on it;
  • the prepared sample is pressurized and solidified.
  • the third aspect of the present invention provides an application of the above-mentioned self-lubricating coating in the fields of aerospace, automobile, biomedicine, petroleum equipment and electronics.
  • the present invention uses carbon fiber cotton as a reinforcing phase, which can be combined with molybdenum disulfide on a surface with a low relative friction coefficient and uniform surface friction performance through an adhesive, which helps to strengthen the tight load between the three.
  • Phenolic acetal has good adhesion and high bonding strength to carbon fiber cotton and molybdenum disulfide
  • phenolic acetal adhesive has the advantages of both phenolic and polyvinyl acetal resins, and has good mechanical strength , Excellent flexibility.
  • the phenolic acetal adhesive has excellent anti-vibration and fatigue resistance, excellent water resistance, moisture and heat aging resistance, especially excellent atmospheric aging resistance, and excellent medium resistance.
  • the invention uses phenolic acetal as an adhesive to assist the compounding of carbon fiber cotton and molybdenum disulfide, so that the finally obtained coating has excellent mechanical strength and self-lubricating effect.
  • Fig. 1 is the sectional view of the self-lubricating coating prepared in Example 1 of the present invention
  • Fig. 2 is a surface view of the self-lubricating coating prepared in Example 1 of the present invention.
  • the present invention proposes a self-lubricating coating, which uses carbon fiber cotton as the material skeleton, and molybdenum disulfide and phenolic acetal adhesive are filled in the skeleton voids.
  • the present invention adopts carbon fiber cotton as matrix carbon material reinforcing phase, because carbon fiber is a kind of high-strength, high-modulus new-type fiber material, and it has the property of "outer softness and inner rigidity", and its quality is lighter than metal aluminum, but its strength is lower. It is higher than steel and has corrosion resistance. It is an important material in national defense and civilian use. It not only has the inherent intrinsic characteristics of carbon materials, but also has the softness and processability of fibers. It is a new generation of reinforcing fibers.
  • the present invention adopts carbon fiber cotton with special fiber arrangement structure instead of other carbon fiber braids, because the fiber direction arrangement in carbon fiber cotton is arbitrary, while the arrangement of fibers in carbon fiber braids is orderly, This orderliness will lead to increased friction along a specific direction, which on the one hand will result in an enhanced surface friction coefficient, and on the other hand will result in uneven surface friction properties.
  • the present invention uses carbon fiber cotton as the reinforcing phase, which can combine the lubricating phase with the lubricating phase with a low relative friction coefficient and uniform surface friction performance through an adhesive, which helps to strengthen the tight load between the three.
  • the present invention uses molybdenum disulfide as a reinforcing phase instead of other lubricating materials such as graphite and talcum powder.
  • molybdenum disulfide is used as a reinforcing phase instead of other lubricating materials such as graphite and talcum powder.
  • the friction coefficient of molybdenum disulfide is lower (0.03-0.06), and the lubricity possessed by molybdenum disulfide is not adsorption. It is caused by a film or gas, and the lubricity is inherent in itself.
  • Molybdenum disulfide is easy to layer, and a layer of molybdenum disulfide protective film is formed on the surface of the reinforcement phase, thereby effectively providing lubrication.
  • the present invention uses phenolic acetal adhesive to bond the reinforcing phase and the lubricating phase, because phenolic acetal has good adhesion and high bonding strength for carbon fiber cotton and molybdenum disulfide, and phenolic acetal adhesive
  • the agent combines the advantages of phenolic and polyvinyl acetal resins, with good mechanical strength and excellent flexibility.
  • the phenolic acetal adhesive has excellent anti-vibration and fatigue resistance, excellent water resistance, moisture and heat aging resistance, especially excellent atmospheric aging resistance, and excellent medium resistance.
  • the invention uses phenolic acetal as an adhesive to assist the compounding of carbon fiber cotton and molybdenum disulfide, so that the finally obtained coating has excellent mechanical strength and self-lubricating effect.
  • the coating material can be applied to transportation, such as brake materials in brakes, clutches and friction transmissions of various machinery and equipment.
  • the reasonable ratio of carbon fiber cotton, molybdenum disulfide, and phenolic acetal adhesive is the premise to ensure that the coating material has excellent mechanical strength and self-lubricating effect. Too much of any component of carbon fiber cotton or molybdenum disulfide will lead to The overall strength and self-lubrication of the coating material are unbalanced, and the amount of phenolic acetal adhesive is too large, which will lead to a decrease in the proportion of the active reinforcing phase and the lubricating phase, making it difficult to obtain a coating material with high strength and self-lubricating properties If there is too little phenolic acetal adhesive, it will be difficult to exert the bonding effect, and carbon fiber cotton and molybdenum disulfide cannot be tightly combined. Therefore, as a preferred embodiment, the quality of carbon fiber cotton, molybdenum disulfide, and phenolic acetal adhesive The ratio is (50-55): (0.9-1.1): (9-11);
  • the mass ratio of carbon fiber cotton, molybdenum disulfide, and phenolic acetal adhesive is 50:1:10;
  • the second aspect of the present invention provides a method for preparing the above-mentioned self-lubricating coating, specifically:
  • Step 1 Measure molybdenum disulfide and phenolic acetal adhesive in a certain proportion and mix them evenly;
  • Step 2 Take an appropriate amount of carbon fiber cotton, and soak the carbon fiber cotton in the adhesive mixed with molybdenum disulfide until it is completely soaked;
  • Step three select a board of appropriate size and place the soaked carbon fiber cotton on it;
  • the prepared sample is pressurized and solidified.
  • the mass ratio of the molybdenum disulfide and the phenolic acetal adhesive is 1:10;
  • the surface of the carbon fiber cotton must be smooth and roughened, and it must be degreased and decontaminated by an organic solvent before soaking.
  • the carbon fiber cotton has a thickness of 2 mm, a gram weight of 1.5 g/10 cm2, and a sample size of 4 cm*25 cm;
  • the organic solvent includes but not limited to ethanol and acetone.
  • the material of the plate is not limited, it is iron plate, aluminum plate, titanium plate and other metal alloy plates;
  • the plate is an aluminum plate, the surface of the plate needs to be chemically treated, and then the soaked carbon fiber cotton is placed on it;
  • the soaked carbon fiber cotton shows that it will be uneven due to the effect of liquid tension. Therefore, the surface of the soaked carbon fiber cotton needs to be evenly painted with glue tools for 2 to 3 times, and each time it is left to air for 20 to 30 minutes ( Wait until the adhesive layer is not sticky);
  • the curing pressure is 0.1-0.2 MPa
  • the curing temperature is 175-185° C.
  • the curing time is 2-3 hours
  • the oven is naturally cooled to room temperature and taken out.
  • the third aspect of the present invention provides an application of the above-mentioned self-lubricating coating in the fields of aerospace, automobile, biomedicine, petroleum equipment and electronics.
  • This embodiment provides a method for preparing a self-lubricating coating, specifically:
  • FIG. 1 The cross-sectional view of the coating material prepared in this embodiment is shown in FIG. 1 , and the surface view is shown in FIG. 2 .
  • carbon fiber cotton For carbon fiber cotton, the surface of carbon fiber cotton is smoothed and roughened, and after degreasing and decontaminating with ethanol, it is soaked in an adhesive mixed with molybdenum disulfide until it is completely soaked;
  • carbon fiber cotton For carbon fiber cotton, the surface of carbon fiber cotton is smoothed and roughened, and after degreasing and decontaminating with ethanol, it is soaked in an adhesive mixed with molybdenum disulfide until it is completely soaked;

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明属于自润滑涂层技术领域，具体涉及一种自润滑涂层及其制备方法与应用。该涂层以碳纤维棉为材料骨架，二硫化钼和酚醛缩醛胶黏剂填充在骨架空隙内；该涂层材料不仅具备较高的机械强度，还能够实现优异的自润滑效果，可作为制动材料广泛应用于各种机器设备的制动器、离合器及摩擦传动装置中。

Description

一种自润滑涂层及其制备方法与应用 技术领域
本发明属于自润滑涂层技术领域，具体涉及一种自润滑涂层及其制备方法与应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
摩擦材料广泛用于各种交通运输工具(如汽车、火车、飞机、舰船等)和各种机器设备的制动器、离合器及摩擦传动装置中的制动材料。在制动装置中，利用摩擦材料的摩擦性能，将转动的动能转化为热能及其他形式的能量，从而使传动装置制动。
基于现代社会对环保与安全的要求越来越高，世界汽车工业发达国家迅速开展了非石棉摩擦材料的研究开发，相继推出了非石棉的半金属型摩擦材料、烧结金属型摩擦材料、代用纤维增强或聚合物粘接摩擦材料、复合纤维摩擦材料、陶瓷纤维摩擦材料等。
自润滑涂层技术是指将固体物质涂或镀于摩擦副界面，作为固体润滑材料或固体润滑剂，对摩擦副界面进行润滑的方法，以降低摩擦或减少摩擦。
在各种摩擦材料中，由于纤维增强摩擦材料中的增强纤维可使材料具有一定的强度、韧性、耐冲击、剪切、拉伸等机械作用而不出现裂纹、断裂、崩缺等机械损伤，因此纤维增强摩擦材料引起了广泛关注。可以用于材料增强的纤 维主要有碳纤维、陶瓷纤维、玻璃纤维、芳纶纤维等。目前，鉴于碳纤维的优异性能，其被作为广泛作为增强相，以二硫化钼、石墨、滑石粉、软金属、金属氧化物作为润滑相，制备具有自润滑功能的碳纤维涂层。增强相与润滑相之间往往需要采用胶黏剂进行粘合，现有的胶粘剂一般为环氧树脂胶黏剂、聚氨酯胶黏剂、聚醋酸乙烯胶黏剂等，然而发明人发现，现有的自润滑碳纤维涂层的机械强度和自润滑效果均比较有限，需要进行进一步探究来获得同时具有高机械强度和自润滑效果的涂层材料。
发明内容
为了解决现有技术的不足，本发明提供一种自润滑涂层及其制备方法与应用，该自润滑涂层以碳纤维棉为增强相、二硫化钼为润滑相、酚醛缩醛为胶黏剂，该涂层材料不仅具备较高的机械强度，还能够实现优异的自润滑效果，可作为制动材料广泛应用于各种机器设备的制动器、离合器及摩擦传动装置中。
为了实现上述目的，本发明第一方面提供一种自润滑涂层，该涂层以碳纤维棉为材料骨架，二硫化钼和酚醛缩醛胶黏剂填充在骨架空隙内。
其中，碳纤维棉、二硫化钼、酚醛缩醛胶黏剂的质量比为(50-55)：(0.9-1.1)：(9-11)。
本发明第二方面提供一种上述自润滑涂层的制备方法，具体为：
工序一，按一定比例量取二硫化钼和酚醛缩醛胶黏剂，并混合均匀；
工序二，取适量的碳纤维棉，将碳纤维棉浸泡于混有二硫化钼的胶粘剂中，直至完全浸透；
工序三，选取适当大小的板材将浸泡好的碳纤维棉置于上面；
工序四，将制好的样品加压固化。
本发明第三方面提供一种上述自润滑涂层在航空航天、汽车、生物医疗、 石油装备和电子领域中的应用。
本发明的一个或多个实施方式至少具有以下有益效果：
(1)本发明采用碳纤维棉作为增强相，能够以相对摩擦系数低，且表面摩擦性能均一的表面与二硫化钼通过胶黏剂复合，有助于加强三者之间的紧密负载。
(2)酚醛缩醛对于碳纤维棉和二硫化钼具有良好的熟附性和很高的胶接强度，而且酚醛缩醛胶黏剂兼具酚醛和聚乙烯醇缩醛树脂的优点，机械强度好，柔韧性优良。另外，酚醛缩醛胶黏剂的抗震动和耐疲劳性能非常优越，具有优异的耐水、耐湿热老化、尤其是耐大气老化性能极为优异、耐介质性能优异。本发明采用酚醛缩醛作为胶黏剂来辅助碳纤维棉和二硫化钼的复合，能够使最终得到的涂层具备优异的机械强度和自润滑效果。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1为本发明实施例1所制备的自润滑涂层的切面图；
图2为本发明实施例1所制备的自润滑涂层的表面图。
具体实施方式
应该指出，以下详细说明都是示例性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说 明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
正如背景技术所介绍的，现有的自润滑碳纤维涂层的机械强度和自润滑效果均比较有限，需要进行进一步探究来获得同时具有高机械强度和自润滑效果的涂层材料。
为了解决如上的技术问题，本发明提出了一种自润滑涂层，该涂层以碳纤维棉为材料骨架，二硫化钼和酚醛缩醛胶黏剂填充在骨架空隙内。
其中，本发明采用碳纤维棉作为基体碳材料增强相，是因为碳纤维是一种高强度、高模量的新型纤维材料，它具有“外柔内刚”性质，质量比金属铝轻，但强度却高于钢铁，并且具有耐腐蚀特性，在国防军工和民用方面都是重要材料。它不仅具有碳材料的固有本征特性，又兼备纤维的柔软可加工性，是新一代增强纤维。而本发明采用具有特殊纤维排布结构的碳纤维棉，而非其他的碳纤维编织物，原因在于碳纤维棉中的纤维方向排布是任意的，而碳纤维编织物中纤维的排布是有序的，这种有序性会导致摩擦力沿某个特定方向上增强，这样一方面或造成表面摩擦系数的增强，另一方面还会导致表面摩擦性能不均匀。本发明采用碳纤维棉作为增强相，能够以相对摩擦系数低，且表面摩擦性能均一的表面与润滑相通过胶黏剂复合，有助于加强三者之间的紧密负载。
本发明以二硫化钼作为增强相，而非石墨、滑石粉等其他润滑材料，一方面是因为二硫化钼的摩擦系数更低(0.03～0.06)，且二硫化钼所具备的润滑性不是吸附膜或气体所致，润滑性是它本身所固有的，二硫化钼是容易分层，在增强相表面形成一层二硫化钼保护膜，进而有效地提供润滑作用。
本发明采用酚醛缩醛胶黏剂将增强相和润滑相进行粘连，是因为酚醛缩醛对于碳纤维棉和二硫化钼具有良好的熟附性和很高的胶接强度，而且酚醛缩醛 胶黏剂兼具酚醛和聚乙烯醇缩醛树脂的优点，机械强度好，柔韧性优良。另外，酚醛缩醛胶黏剂的抗震动和耐疲劳性能非常优越，具有优异的耐水、耐湿热老化、尤其是耐大气老化性能极为优异、耐介质性能优异。本发明采用酚醛缩醛作为胶黏剂来辅助碳纤维棉和二硫化钼的复合，能够使最终得到的涂层具备优异的机械强度和自润滑效果。
涂层摩擦时，碳纤维棉作为材料的骨架主要起到增强涂层的强度、模量、耐冲击性能，使其不出现裂纹等破坏。另外涂层摩擦时碳纤维棉受到挤压时，二硫化钼被挤压到表面，二硫化钼是一种层状的化合物非常容易分层，在碳纤维表面形成一层二硫化钼保护膜，二硫化钼摩擦系数低，摩擦阻力小可有效地为涂层提供润滑。因此，该涂层材料可应用于交通运输，比如各种机器设备的制动器、离合器及摩擦传动装置中的制动材料。
碳纤维棉、二硫化钼、酚醛缩醛胶黏剂的合理配比是保证涂层材料具有优异机械强度和自润滑效果的前提，碳纤维棉或二硫化钼任何一种组分的偏多，都会导致涂层材料整体强度和自润滑性的失衡，而酚醛缩醛胶黏剂的量偏多则会导致活性增强相和润滑相的占比减小，难以获得高强度和自润滑特性的涂层材料，酚醛缩醛胶黏剂的偏少则难以发挥粘合效果，碳纤维棉与二硫化钼无法紧密复合，因此，作为优选的实施方式，碳纤维棉、二硫化钼、酚醛缩醛胶黏剂的质量比为(50-55)：(0.9-1.1)：(9-11)；
进一步的，碳纤维棉、二硫化钼、酚醛缩醛胶黏剂的质量比为50：1：10；
本发明第二方面提供一种上述自润滑涂层的制备方法，具体为：
工序一，按一定比例量取二硫化钼和酚醛缩醛胶黏剂，并混合均匀；
工序二，取适量的碳纤维棉，将碳纤维棉浸泡于混有二硫化钼的胶粘剂中，直至完全浸透；
工序三，选取适当大小的板材将浸泡好的碳纤维棉置于上面；
工序四，将制好的样品加压固化。
其中，
为了得到上述特定配比的涂层材料，所述二硫化钼与酚醛缩醛胶黏剂的质量比为1:10；
为了使碳纤维棉呈现洁净、平整的表面，使其与二硫化钼能够进行紧密复合，作为优选的实施方式，碳纤维棉表面须平整、打毛，且通过有机溶剂脱脂、去污后再进行浸泡。
在本发明的一种或多种实施方式中，所述碳纤维棉的规格为厚度2mm，克重1.5克/10平方厘米，试样大小为4cm*25cm；
进一步的，所述有机溶剂包括但不限于乙醇、丙酮。
进一步的，所述板材的材质不限，为铁板、铝板、钛板及其他金属合金板；
若板材为铝板，则需要将板材表面进行化学处理，然后再将浸泡好的碳纤维棉置于上面；
浸泡好的碳纤维棉，表明由于液体张力的作用会出现不均匀的现象，因此，浸泡好的碳纤维棉表面需要采用涂胶工具均匀涂刷2～3次，每次间隔晾置20～30分钟(等胶层不粘)；
在本发明的一种或多种实施方式中，所述固化压力为0.1～0.2MPa，固化温度为175-185℃，固化时间为2-3小时，待烘箱温度自然冷却至室温取出。
本发明第三方面提供一种上述自润滑涂层在航空航天、汽车、生物医疗、石油装备和电子领域中的应用。
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例与对比例详细说明本发明的技术方案。
实施例1
本实施例提供一种自润滑涂层的制备方法，具体为：
(1)按1：10的质量比量取二硫化钼和酚醛缩醛胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)，将碳纤维棉表面修建平整、打毛，并通过乙醇脱脂、去污后，浸泡于混有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.2MPa下，于180℃加压固化2小时，待烘箱温度自然冷却至室温取出。
本实施例制备得到的涂层材料的切面图如图1所示，表面图如图2所示。
实施例2
(1)按0.9：10的质量比量取二硫化钼和酚醛缩醛胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)，将碳纤维棉表面修建平整、打毛，并通过丙酮脱脂、去污后，浸泡于混有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.1MPa下，于180℃加压固化3小时，待烘箱温度自然冷却至室温取出。
实施例3
(1)按1：11的质量比量取二硫化钼和酚醛缩醛胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)，将碳纤维棉表面修建平整、打毛，并通过乙醇脱脂、去污后，浸泡于混有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.2MPa下，于175℃加压固化2小时，待烘箱温度自然冷却至室温取出。
实施例4
(1)按1：10的质量比量取二硫化钼和酚醛缩醛胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)，将碳纤维棉表面修建平整、打毛，并通过乙醇脱脂、去污后，浸泡于混有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.1MPa下，于185℃加压固化2小时，待烘箱温度自然冷却至室温取出。
对比例1
(1)按1：10的质量比量取二硫化钼和酚醛树脂胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)，将碳纤维棉表面修建平整、打毛，并通过乙醇脱脂、去污后，浸泡于混 有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.2MPa下，于180℃加压固化2小时，待烘箱温度自然冷却至室温取出。
对比例2
(1)按1：10的质量比量取二硫化钼和聚乙烯醇缩醛胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)，将碳纤维棉表面修建平整、打毛，并通过乙醇脱脂、去污后，浸泡于混有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.2MPa下，于180℃加压固化2小时，待烘箱温度自然冷却至室温取出。
对比例3
(1)按1：10的质量比量取二硫化钼和聚醋酸乙烯胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)，将碳纤维棉表面修建平整、打毛，并通过乙醇脱脂、去污后，浸泡于混有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.2MPa下，于180℃加压固化2小时，待烘箱温度自然冷却至室温取出。
对比例4
(1)按1：10的质量比量取石墨和酚醛缩醛胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)；
碳纤维棉，将碳纤维棉表面修建平整、打毛，并通过乙醇脱脂、去污后，浸泡于混有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.2MPa下，于180℃加压固化2小时，待烘箱温度自然冷却至室温取出。
对比例5
(1)按1：10的质量比量取滑石粉和酚醛缩醛胶黏剂，并混合均匀；
(2)取大小为4cm*25cm的碳纤维棉(规格：厚度2mm，1.5克/10平方厘米)；
碳纤维棉，将碳纤维棉表面修建平整、打毛，并通过乙醇脱脂、去污后，浸泡于混有二硫化钼的胶黏剂中，直至完全浸透；
(3)浸泡好的碳纤维棉，表面采用油画笔均匀涂刷3次，每次间隔晾置20分钟，等胶层不粘；
(4)选取适当大小的板材将涂刷好的碳纤维棉置于上面；
(5)将制好的样品在0.2MPa下，于180℃加压固化2小时，待烘箱温度自然冷却至室温取出。
性能测试：
表1采用不同黏合剂碳纤维涂层剥离强力对比
Figure PCTCN2021098976-appb-000001
从表1数据可以看出采用酚醛缩醛胶黏剂碳纤维涂层剥离强力最高，机械性能最好，且不匀系数最低，均匀度好。
表2采用不同黏合剂和润滑材料的碳纤维涂层摩擦系数对比(压力20N)
Figure PCTCN2021098976-appb-000002
从表2数据可以看出，一方面，针对同一种润滑相碳纤维棉涂层，随着胶黏剂的变化，摩擦系数的值也是变化的，在采用酚醛缩醛作为胶黏剂的时候， 摩擦系数最小，说明具有最优异的自润滑效果；另一方面，针对同一种胶黏剂来说，当变换润滑相时，摩擦系数也是发生变化的，这说明，润滑相的选择也会对涂层的自润滑效果造成影响。因此，本发明所获得的高自润滑性的涂层源于润滑相和胶黏剂的共同作用，在以二硫化钼作为润滑相，以酚醛缩醛作为胶黏剂的情况下，碳纤维棉涂层的摩擦系数最低，使摩擦设备间产生的摩擦阻力最小。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种自润滑涂层，其特征在于：该涂层以碳纤维棉为材料骨架，二硫化钼和酚醛缩醛胶黏剂填充在骨架空隙内。
  2. 如权利要求1所述的自润滑涂层，其特征在于：碳纤维棉、二硫化钼、酚醛缩醛胶黏剂的质量比为(50-55)：(0.9-1.1)：(9-11)；
    优选的，碳纤维棉、二硫化钼、酚醛缩醛胶黏剂的质量比为50：1：10。
  3. 一种权利要求1或2所述的自润滑涂层的制备方法，其特征在于：
    工序一，按一定比例量取二硫化钼和酚醛缩醛胶黏剂，并混合均匀；
    工序二，取适量的碳纤维棉，将碳纤维棉浸泡于混有二硫化钼的胶粘剂中，直至完全浸透；
    工序三，选取适当大小的板材将浸泡好的碳纤维棉置于上面；
    工序四，将制好的样品加压固化。
  4. 如权利要求3所述的制备方法，其特征在于：所述二硫化钼与酚醛缩醛胶黏剂的质量比为1:10。
  5. 如权利要求3所述的制备方法，其特征在于：所述碳纤维棉表面须平整、打毛，且通过有机溶剂脱脂、去污后再进行浸泡。
  6. 如权利要求3所述的制备方法，其特征在于：所述板材为铁板、铝板、钛板及金属合金板；
    若板材为铝板，则需要将板材表面进行化学处理，然后再将浸泡好的碳纤维棉置于上面。
  7. 如权利要求3所述的制备方法，其特征在于：所述碳纤维棉的规格为：厚度2mm，克重1.5克/10平方厘米，试样大小为4cm*25cm；
    所述有机溶剂包括但不限于乙醇、丙酮。
  8. 如权利要求3所述的制备方法，其特征在于：泡好的碳纤维棉表面需要采 用涂胶工具均匀涂刷2～3次，每次间隔晾置20～30分钟。
  9. 如权利要求3所述的制备方法，其特征在于：所述固化温度为175-185℃，固化时间为2-3小时，待烘箱温度自然冷却至室温取出。
  10. 权利要求1或2所述的自润滑涂层在航空航天、汽车、生物医疗、石油装备和电子领域中的应用。
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