CN114086424A - MOF-5/dopamine double-effect enhanced paper-based friction material and preparation method thereof - Google Patents

MOF-5/dopamine double-effect enhanced paper-based friction material and preparation method thereof Download PDF

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CN114086424A
CN114086424A CN202111309803.1A CN202111309803A CN114086424A CN 114086424 A CN114086424 A CN 114086424A CN 202111309803 A CN202111309803 A CN 202111309803A CN 114086424 A CN114086424 A CN 114086424A
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fiber
drying
mof
solution
dopamine
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李贺军
马珊珊
费杰
齐乐华
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Northwestern Polytechnical University
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
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    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
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    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance

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Abstract

The invention relates to an MOF-5/dopamine double-effect enhanced paper-based friction material and a preparation method thereof, wherein carbon fibers are soaked and cleaned by acetoneWashing to remove sizing agent and other impurities on the surface of the fiber; placing the carbon fibers with clean surfaces into a solution of tris (hydroxymethyl) aminomethane and dopamine in sequence to form a layer of highly-adhered dopamine flexible film on the surfaces of the carbon fibers; and then growing an MOF-5 crystal layer on the surface of the carbon fiber in situ based on a hydrothermal reaction, and fully washing and drying the modified carbon fiber after the reaction is finished. The modified carbon fiber and a resin matrix are adopted to construct a double-effect enhanced interface structure, and the MOF-5/dopamine double-effect enhanced paper-based friction material is prepared. The dynamic friction coefficient of the MOF-5/dopamine double-effect enhanced paper-based friction material prepared by the method is improved from 0.1068 to 0.1279, and the increase is 19.76%. The wear rate is 3.55 multiplied by 10‑8cm3·J‑1Down to 3.00X 10‑8cm3·J‑1The amplitude reduction is 15.49%. The double-effect enhancement effect of the MOF-5/dopamine on mechanical interlocking and chemical coupling mechanisms is fully displayed, and the friction and wear performance of the paper-based friction material can be remarkably improved when the paper-based friction material is applied to the paper-based friction material.

Description

MOF-5/dopamine double-effect enhanced paper-based friction material and preparation method thereof
Technical Field
The invention belongs to the technical field of friction materials, and relates to an MOF-5/dopamine double-effect enhanced paper-based friction material and a preparation method thereof.
Background
The paper-based friction material is prepared by using carbon fibers, aramid fibers, plant fibers, a friction performance regulator, a resin binder and the like as main raw materials through wet papermaking, vacuum filtration and hot-pressing curing. The brake has the excellent characteristics of stable braking process, low noise, long service life and the like, and is widely applied to transmission and braking devices of vehicles. However, due to the smooth surface and strong chemical inertness, the high-strength and high-modulus carbon fibers are difficult to form effective combination with the resin matrix, thereby seriously affecting the performance of the friction material. In the actual working condition operation process, under the conditions of heavy load, high pressure and high rotating speed, the conditions of carbon fiber breakage and extraction, resin matrix debonding and the like often occur, and the wide application of the low-cost paper-based friction material is further limited. Therefore, the problems of improving the compatibility of the carbon fiber and the resin matrix and improving the poor interface bonding performance become the bottleneck and key point for limiting the development of the paper-based friction material.
Document 1, chinese patent No. CN106868902A, discloses a method for preparing a sheet-like self-assembled manganese dioxide modified carbon fiber reinforced resin-based friction material. Potassium permanganate and concentrated sulfuric acid are used for growing flaky manganese dioxide on the surface of carbon fiber by utilizing redox reaction, and the flaky manganese dioxide is used as a friction material reinforcement and is applied to a wet resin-based friction material. Although the single oxide growth is beneficial to improving the interface performance of the resin matrix composite material to a certain extent, compared with single-component improvement, the double-component synergistic modified carbon fiber is more effective in enhancing the interface combination between the carbon fiber and the resin matrix based on the mechanical meshing and chemical coupling effects, and further improves the tribological performance of the material. In addition, concentrated sulfuric acid is adopted to pretreat the carbon fiber to improve the surface roughness and chemical activity of the carbon fiber, but the problem of serious damage to the fiber body exists.
Document 2, chinese patent No. CN110016807A, discloses a surface modification method for carbon fiber surface functionalization. The invention adopts dopamine as a surface modifier to achieve the purpose of functionalizing the surface of the carbon fiber, thereby improving the interface compatibility of the carbon fiber and a resin matrix. Although the dopamine treatment can improve the surface activity of the carbon fiber and promote the interface bonding of the carbon fiber and a resin matrix to be enhanced, the dopamine is usually attached to the surface of the fiber in the form of a sheet film and cannot be effectively and mechanically engaged with the fiber or the matrix, so that the resin-based composite material still has the conditions of fiber extraction, matrix fracture and the like under the action of high-pressure heavy load in the actual application process.
Document 3, chinese patent No. CN108439457A, discloses a method for preparing a zinc oxide nanorod/carbon cloth friction material by a hydrothermal electrophoresis method. The invention adopts a hydrothermal electrophoresis method to grow zinc oxide nano rods on the surface of carbon cloth, then vacuum impregnation of phenolic resin is carried out, and finally high-temperature hot-press molding is carried out. The method effectively improves the interface combination of the carbon cloth and the resin, thereby improving the frictional wear performance of the resin-based friction material. However, the zinc oxide nano rod belongs to inorganic nonmetallic minerals, and the zinc oxide nano rod is lack of active groups, so that the modified carbon cloth cannot form effective chemical bonding with a resin matrix, and the process of growing the zinc oxide nano rod by adopting a hydrothermal electrophoresis method is complex and has large energy consumption.
In the above-listed documents and most of other patent documents in the same field, single reinforcement such as manganese dioxide, dopamine, zinc oxide and the like is usually adopted to improve the interface bonding performance of the resin-based composite material, and the problems of poor single-component reinforcement effect, poor friction coefficient stability, high-temperature heat fading and the like still exist. Meanwhile, the strong acid pretreatment of the carbon fiber can improve the surface activity, but the internal structure of the carbon fiber can be seriously damaged and the strength of the carbon fiber can be damaged in the process. In the prior art, the research on improving the interface bonding performance of a resin-based composite material is concentrated on single-component reinforcement, the double-component synergistic modification and simple and effective preparation process of a paper-based friction material are deficient, and the urgent need is to develop a method for improving the interface bonding of a double-effect synergistic modified carbon fiber reinforced paper-based friction material, maintain the strength performance of a carbon fiber body and comprehensively improve the friction and wear performance of the paper-based friction material. At present, related researches on the aspects of enhancing the paper-based friction material by using the MOF-5 and dopamine are not carried out.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides an MOF-5/dopamine double-effect enhanced paper-based friction material and a preparation method thereof, wherein dopamine is firstly adopted to pretreat carbon fibers, and reactive active sites are provided for the subsequent MOF-5 crystal growth while active functional groups are endowed to the surface of the carbon fibers. By utilizing a hydrothermal reaction, the MOF-5 grows on the surface of the carbon fiber in situ, so that the MOF-5 and dopamine form a double-effect modified carbon fiber to achieve the purpose of activating the carbon fiber and endow part of active reaction groups on the surface of the inert fiber. And then growing the MOF-5 crystals on the surface of the carbon fibers by using an in-situ growth technology and a hydrothermal method to obtain the MOF-5 crystal modified carbon fibers, and then performing wet forming, vacuum filtration, resin impregnation and hot-pressing curing to prepare the MOF-5/dopamine double-effect enhanced paper-based friction material. The high-adhesiveness dopamine is wrapped on the surface of the carbon fiber, so that on one hand, the surface roughness of the smooth carbon fiber can be increased, and meanwhile, the high-adhesiveness dopamine can play a role in improving the surface activity of the fiber due to the fact that the high-adhesiveness dopamine has active groups. On the other hand, the direct growth of the crystals on the surface of the carbon fiber is limited by the strong inertia of the surface, and the pretreatment of the dopamine can effectively improve and relieve the problem, and simultaneously provides a favorable growth platform for the subsequent growth of the MOF-5 crystals. The MOF-5 crystal grown in situ has abundant metal active sites and a large number of active groups, so that the chemical bonding between the fiber and the resin matrix can be effectively promoted. Therefore, the MOF-5/dopamine double-effect modified carbon fiber can enhance the mechanical interlocking between the carbon fiber and a resin matrix and promote the effective chemical coupling between the carbon fiber and the resin matrix, thereby remarkably improving the interface compatibility and interlayer bonding of the fiber and the matrix and finally improving the friction and wear performance of the paper-based friction material.
Technical scheme
An MOF-5/dopamine double-effect reinforced paper-based friction material comprises carbon fibers, aramid fibers, paper pulp fibers and a filler; the method is characterized in that the carbon fiber is subjected to double modification by MOF-5 and dopamine, and the surface of the carbon fiber has active functional groups which become reactive active sites for MOF-5 crystal growth; the MOF-5 grows on the surface of the carbon fiber in situ, and forms double-effect modified carbon fiber with dopamine, mechanical interlocking occurs between the reinforced carbon fiber and a resin matrix, effective chemical coupling is formed between the reinforced carbon fiber and the resin matrix, and the compatibility of the fiber and the matrix interface and interlayer combination are realized, so that the dynamic friction coefficient is improved by 19.76%; the wear rate is reduced by 15.49%; the mass ratio of the modified carbon fiber, the aramid fiber, the paper pulp fiber and the filler is 1.0-1.4: 1.3-1.6: 2.5-3.0, and the sum of the mass percentages is 100%.
The filler includes, but is not limited to, barium sulfate, graphite, alumina, chromite, fluorite powder, montmorillonite or talc.
A method for preparing the MOF-5/dopamine double-effect reinforced paper-based friction material is characterized by comprising the following steps:
step 1, carrying out double modification on carbon fibers:
step 1), soaking and cleaning carbon fibers with acetone, removing sizing agent and other impurities on the surfaces of the fibers, and drying to obtain carbon fibers I with clean surfaces;
step 2), dissolving Tris (hydroxymethyl) aminomethane buffer solution in deionized water at room temperature, performing magnetic stirring to obtain solution A, dissolving dopamine in deionized water, and performing ultrasonic dispersion to obtain solution B;
the mass concentration of the dopamine in the solution B is 1.8-2.4%;
step 3), adjusting the pH value of the solution A to 8-9 by adopting acid, and pouring the solution B into the solution A in the process of magnetic continuous stirring to fully mix the solution A; placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, and drying for later use after the reaction is finished to obtain carbon fiber II;
step 4), dissolving zinc nitrate hexahydrate in N, N-dimethylformamide DMF at room temperature to obtain a solution C, and dissolving terephthalic acid in DMF to obtain a solution D;
the mass concentration of zinc nitrate hexahydrate in the solution C is 8.4-14.8%;
the mass concentration of the terephthalic acid in the solution D is 3.7-11.6%;
step 5), placing the carbon fiber II in the step three into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step 6), after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step 7), pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting for 24-48 h in an oil bath at 120-150 ℃, separating fibers loaded with MOF-5 crystals by a vacuum filtration method after the reaction is finished, cleaning the fibers loaded with the MOF-5 crystals for a plurality of times by using DMF, and drying to obtain an MOF-5/dopamine modified carbon fiber III;
step 2: carrying out defibering on the MOF-5/dopamine modified carbon fiber III, aramid fiber and pulp fiber to prepare a fiber mixed solution, adding a filler, preparing a wet sample sheet by a vacuum filtration principle and a pulping and papermaking mode, and drying the wet sample sheet in an oven;
the mass ratio of the carbon fiber III to the aramid fiber to the paper pulp fiber to the filler is 1.0-1.4: 1.3-1.6: 2.5-3.0;
and step 3: and (3) dipping the dry sample obtained in the step (2) in modified phenolic resin, and drying at room temperature after completion, wherein the hot-pressing curing temperature is 130-150 ℃, the curing time is 3-10 min, and the curing pressure is 5-15 Pa, so that the hot-pressing curing treatment is completed, and the MOF-5/dopamine double-effect reinforced paper-based friction material is obtained.
The step 1) is to put the carbon fiber into an acetone solution to be soaked for 12-48 h, wherein the drying temperature is 80-150 ℃, and the drying time is 12-24 h.
The mass concentration of the Tris buffer solution in the solution A in the step 2) is 1.0-2.0%.
The acid regulating solution of step 3) includes, but is not limited to, hydrochloric acid, acetic acid or sulfuric acid.
The magnetic stirring revolution in the step 3) is 1000-1500r, the drying temperature is 80-150 ℃, and the drying time is 12-24 h.
The drying mode of the carbon fiber III in the step 7) comprises freeze drying, oven drying or normal temperature drying; when freeze-dried: the drying temperature is-45 to-65 ℃, the drying time is 48 to 56 hours, and the vacuum degree in the drying process is 15 to 25 Pa; when the oven is dry: the drying temperature is 70-105 ℃, and the drying time is 12-24 h.
And (3) drying the oven in the step (2) at the drying temperature of 50-75 ℃ for 1-4 h.
In the step 3, the impregnation concentration of the modified phenolic resin is 10-30%.
Advantageous effects
The invention provides an MOF-5/dopamine double-effect enhanced paper-based friction material and a preparation method thereof,
compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, the MOF-5/dopamine double-effect reinforced carbon fiber reinforced resin-based friction material is adopted, and the synergistic enhancement mechanism of mechanical meshing and chemical bonding is utilized, so that the interfacial property between carbon fibers and a resin matrix is obviously improved, and the aim of improving the frictional wear property of the paper-based friction material is finally achieved.
(1) Compared with the commonly adopted acid etching pretreatment of carbon fiber, the dopamine pretreatment has the advantages that: the fiber can not damage and destroy the internal structure and the strength of the fiber body in the process, and simultaneously, the fiber is wrapped on the surface of the fiber to form a nano-layered substance, so that the surface active groups are endowed to play a role in activating the carbon fiber. In addition, because the dopamine has functional groups such as carboxyl and imino, the dopamine film layer adhered to the surface of the fiber can provide favorable active sites for the in-situ growth of the subsequently modified MOF-5 crystal.
(2) The invention adopts MOF-5 crystal reinforcement, and is beneficial to promoting the formation of effective chemical bonding between fibers and a matrix due to the surface of the MOF-5 crystal reinforcement which has abundant metal open sites and reactive groups. Meanwhile, the MOF-5 crystals are distributed on the surface of the carbon fiber to form a large number of micro-convex structures, and the micro-convex structures can increase the effective contact area between the fiber and the resin and further promote the compatibility of the carbon fiber and a matrix. In addition, the crystal position on the surface of the carbon fiber is used as a physical effective anchor point, and the mechanical meshing action between the carbon fiber and the matrix is obviously enhanced. Therefore, the MOF-5/dopamine double-effect reinforced carbon fiber reinforced resin-based friction material is favorable for good combination between carbon fibers and resin matrix layers based on the principles of physical mechanical engagement and chemical coupling, forms a stable interface buffer area, and reduces and prevents the phenomena of fiber fracture, complete matrix debonding and the like.
Compared with a blank friction material sample, the MOF-5/dopamine double-effect enhanced paper-based friction material prepared by the invention has the advantages that the dynamic friction coefficient is improved by 19.76%; the wear rate is reduced by 15.49%, and excellent frictional wear performance is shown.
Drawings
FIG. 1 is a schematic diagram of a MOF-5/dopamine double-effect modified reinforced carbon fiber mechanism;
FIG. 2 is a comparison of the micro-morphology of the virgin carbon fiber of example 1 and the MOF-5/dopamine dual effect modified carbon fiber of example 3 (a-example 1; b-example 3; a:. times.5000; b:. times.5000);
FIG. 3 is a comparison of the topography of the cross-sections of the blank sample of example 7 and the MOF-5/dopamine dual effect enhanced sample of example 3 after a tensile test (a, b-example 1; c, d-example 3; a:. times.200, b:. times.1000; c: X200, d: X1000);
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the embodiment of the invention adopts the following technical scheme, comprising the following steps:
the method comprises the following steps: soaking 15g of carbon fibers in acetone for 12-48 h, removing a sizing agent and other impurities on the surfaces of the fibers, washing the fibers for 3-5 times by using deionized water, drying the fibers in an oven at the temperature of 80-150 ℃ for 12-24h, and drying the fibers to obtain carbon fibers I with clean surfaces;
step two: dissolving 1.0-2.0 g of Tris (hydroxymethyl) aminomethane (Tris buffer) in 0.97-1.45L of deionized water at room temperature, performing magnetic stirring to obtain a solution A, dissolving 1.8-2.2 g of dopamine in 0.03-0.05L of deionized water, and performing ultrasonic dispersion to obtain a solution B;
step three: and (3) adjusting the pH value of the solution A to 8-9 by using hydrochloric acid, pouring the solution B into the solution A to fully mix the solution B when the magnetic stirring revolution is 1000-1500r in the magnetic continuous stirring process. Placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, drying in a drying oven at 80-150 ℃ for 12-24h after the reaction is finished, and obtaining carbon fiber II for later use;
step four: dissolving 1.04-1.34 g of zinc nitrate hexahydrate in 9-12 g of DMF at room temperature to obtain a solution C, wherein the mass concentration of the zinc nitrate hexahydrate is 8.4-14.8%; dissolving 1.5-3.5 g of terephthalic acid in 30-40 g of DMF to obtain a solution D, wherein the mass concentration of the terephthalic acid is 3.7-11.6%;
step five: placing the carbon fiber II in the third step into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step six: after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step seven: and pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting in a water bath environment, wherein the oil bath temperature is 120-150 ℃, the reaction time is 24-48 h, after the reaction is finished, separating the fiber loaded with the MOF-5 crystal by a vacuum filtration method, cleaning the fiber loaded with the MOF-5 crystal for a plurality of times by using DMF (dimethyl formamide), drying for later use, and performing freeze drying (the drying temperature is-45 to-65 ℃, the drying time is 48-56 h, the vacuum degree in the drying process is 15-25 Pa), oven drying (the drying temperature is 70-105 ℃, and the drying time is 12-24 h) and normal-temperature drying. Obtaining carbon fiber III;
step eight: carrying out defibering on the carbon fiber III, the aramid fiber and the pulp fiber loaded with the MOF-5 crystal obtained in the seventh step to prepare a fiber mixed solution, wherein the mass ratio of the carbon fiber III to the aramid fiber to the pulp fiber to the filler is 1.0-1.4: 1.0-1.4: 1.3-1.6: 2.5-3.0, wherein the sum of the mass percentages is 100%. Adding fillers including but not limited to barium sulfate, graphite, aluminum oxide, chromite, fluorite powder, montmorillonite and talcum powder, preparing a wet sample sheet by using the principle of vacuum filtration and a pulping and papermaking mode, drying the wet sample sheet in an oven at the temperature of 50-75 ℃ for 1-4 hours to obtain a dry sample sheet for later use;
step nine: and (5) dipping the dry sample obtained in the step eight in modified phenolic resin, wherein the dipping concentration is 10-30%, drying at room temperature after completion, and carrying out hot pressing curing treatment, wherein the hot pressing temperature is 130-150 ℃, the curing time is 3-10 min, and the pressure is 5-15 Pa. Thereby obtaining the MOF-5/dopamine double-effect modified paper-based friction material.
Referring to fig. 1, an MOF-5/dopamine double-effect enhanced paper-based friction material and a preparation method thereof comprise the following steps:
the method comprises the following steps: soaking 15g of carbon fibers in acetone for 12-48 h, removing a sizing agent and other impurities on the surfaces of the fibers, washing the fibers for 3-5 times by using deionized water, drying the fibers in an oven at the temperature of 80-150 ℃ for 12-24h, and drying the fibers to obtain carbon fibers I with clean surfaces;
step two: dissolving 1.0-2.0 g of Tris (hydroxymethyl) aminomethane (Tris buffer) in 0.97-1.45L of deionized water at room temperature, performing magnetic stirring to obtain a solution A, dissolving 1.8-2.2 g of dopamine in 0.03-0.05L of deionized water, and performing ultrasonic dispersion to obtain a solution B;
step three: and (3) adjusting the pH value of the solution A to 8-9 by using hydrochloric acid, pouring the solution B into the solution A to fully mix the solution B when the magnetic stirring revolution is 1000-1500r in the magnetic continuous stirring process. Placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, drying in a drying oven at 80-150 ℃ for 12-24h after the reaction is finished, and obtaining carbon fiber II for later use;
step four: dissolving 1.04-1.34 g of zinc nitrate hexahydrate in 9-12 g of DMF at room temperature to obtain a solution C, wherein the mass concentration of the zinc nitrate hexahydrate is 8.4-14.8%; dissolving 1.5-3.5 g of terephthalic acid in 30-40 g of DMF to obtain a solution D, wherein the mass concentration of the terephthalic acid is 3.7-11.6%;
step five: placing the carbon fiber II in the third step into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step six: after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step seven: and pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting in a water bath environment, wherein the oil bath temperature is 120-150 ℃, the reaction time is 24-48 h, after the reaction is finished, separating the fiber loaded with the MOF-5 crystal by a vacuum filtration method, cleaning the fiber loaded with the MOF-5 crystal for a plurality of times by using DMF (dimethyl formamide), drying for later use, and performing freeze drying (the drying temperature is-45 to-65 ℃, the drying time is 48-56 h, the vacuum degree in the drying process is 15-25 Pa), oven drying (the drying temperature is 70-105 ℃, and the drying time is 12-24 h) and normal-temperature drying. Obtaining carbon fiber III;
step eight: carrying out defibering on the carbon fiber III, the aramid fiber and the pulp fiber loaded with the MOF-5 crystal obtained in the seventh step to prepare a fiber mixed solution, wherein the mass ratio of the carbon fiber III to the aramid fiber to the pulp fiber to the filler is 1.0-1.4: 1.0-1.4: 1.3-1.6: 2.5-3.0, wherein the sum of the mass percentages is 100%. Adding fillers including but not limited to barium sulfate, graphite, aluminum oxide, chromite, fluorite powder, montmorillonite and talcum powder, preparing a wet sample sheet by using the principle of vacuum filtration and a pulping and papermaking mode, drying the wet sample sheet in an oven at the temperature of 50-75 ℃ for 1-4 hours to obtain a dry sample sheet for later use;
step nine: and (5) dipping the dry sample obtained in the step eight in modified phenolic resin, wherein the dipping concentration is 10-30%, drying at room temperature after completion, and carrying out hot pressing curing treatment, wherein the hot pressing temperature is 130-150 ℃, the curing time is 3-10 min, and the pressure is 5-15 Pa. Thereby obtaining the MOF-5/dopamine double-effect reinforced paper-based friction material.
The present invention is described in further detail below with reference to specific examples:
example 1 blank example and blank paper-based friction material without carbon fiber modification in the prior art
The method comprises the following steps: carrying out defibering on carbon fibers, aramid fibers and pulp fibers to prepare a fiber mixed solution, wherein the mass ratio of the carbon fibers, the aramid fibers, the pulp fibers and the filler is 1.2: 1.0: 1.3: 3.0, adding a filler comprising barium sulfate, graphite, aluminum oxide and talcum powder, preparing a wet sample sheet by using the principle of vacuum filtration and a pulping and papermaking mode, and drying the wet sample sheet in an oven at the temperature of 75 ℃ for 4 hours to obtain a dry sample sheet for later use;
step two: and (3) soaking the dry sample obtained in the step one in modified phenolic resin, wherein the soaking concentration is 20%, drying at room temperature after completion, and carrying out hot-pressing curing treatment, wherein the hot-pressing temperature is 150 ℃, the curing time is 5min, and the pressure is 15 Pa. Thereby obtaining a blank paper-based friction material.
Detailed description of the invention
Example 2
The method comprises the following steps: soaking 15g of carbon fiber in acetone for 24 hours, removing a sizing agent and other impurities on the surface of the fiber, washing for 3 times by using deionized water after the completion, drying in an oven at the temperature of 80 ℃ for 12 hours, and drying to obtain carbon fiber I with a clean surface;
step two: dissolving 1.0g of Tris (hydroxymethyl) aminomethane (Tris buffer) in 0.97L of deionized water at room temperature, performing magnetic stirring to obtain a solution A, dissolving 1.8g of dopamine in 0.03L of deionized water, and performing ultrasonic dispersion to obtain a solution B;
step three: adjusting the pH value of the solution A to 8 by adopting hydrochloric acid, pouring the solution B into the solution A to be fully mixed when the magnetic stirring revolution is 1000r in the process of magnetic continuous stirring. Placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, and drying in a drying oven at 80 ℃ for 12 hours after the reaction is finished to obtain carbon fiber II for later use;
step four: dissolving 1.04g of zinc nitrate hexahydrate in 9g of DMF (dimethyl formamide) at room temperature to obtain a solution C, wherein the mass concentration of the zinc nitrate hexahydrate is 8.4%; dissolving 1.5g of terephthalic acid in 30g of DMF to obtain a solution D, wherein the mass concentration of the terephthalic acid is 5%;
step five: placing the carbon fiber II in the third step into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step six: after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step seven: and pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting in an oil bath environment at the temperature of 120 ℃ for 24h, separating the fiber loaded with the MOF-5 crystal by a vacuum filtration method after the reaction is finished, washing the fiber loaded with the MOF-5 crystal for a plurality of times by using deionized water, drying for later use, and freeze-drying (the drying temperature is-56 ℃, the drying time is 48h, and the vacuum degree in the drying process is 15 Pa). Obtaining carbon fiber III;
step eight: carrying out defibering on the carbon fiber III, the aramid fiber and the pulp fiber loaded with the MOF-5 crystal obtained in the seventh step to prepare a fiber mixed solution, wherein the mass ratio of the carbon fiber III to the aramid fiber to the pulp fiber to the filler is 1.2: 1.0: 1.3: 3.0, wherein the sum of the mass percentages is 100%. Adding a filler comprising barium sulfate, graphite, aluminum oxide and talcum powder, preparing a wet sample sheet by using the principle of vacuum filtration and a pulping and papermaking mode, and drying the wet sample sheet in an oven at the temperature of 75 ℃ for 4 hours to obtain a dry sample sheet for later use;
step nine: and (5) dipping the dry sample obtained in the step eight in modified phenolic resin, wherein the dipping concentration is 20%, drying at room temperature after completion, and carrying out hot-pressing curing treatment, wherein the hot-pressing temperature is 150 ℃, the curing time is 3min, and the pressure is 15 Pa. Thereby obtaining the MOF-5/dopamine double-effect reinforced paper-based friction material.
Example 3
The method comprises the following steps: soaking 15g of carbon fiber in acetone for 32h, removing sizing agent and other impurities on the surface of the fiber, washing for 3 times by using deionized water after the completion, drying in an oven at 85 ℃ for 18h, and drying to obtain carbon fiber I with a clean surface;
step two: dissolving 1.2g of Tris (hydroxymethyl) aminomethane (Tris buffer) in 0.97L of deionized water at room temperature, performing magnetic stirring to obtain a solution A, dissolving 1.9g of dopamine in 0.03L of deionized water, and performing ultrasonic dispersion to obtain a solution B;
step three: adjusting the pH value of the solution A to 8.5 by using hydrochloric acid, pouring the solution B into the solution A to fully mix the solution B, wherein the magnetic stirring revolution number is 1500r in the process of magnetic continuous stirring. Placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, and drying in a drying oven at 90 ℃ for 16 hours after the reaction is finished to obtain carbon fiber II for later use;
step four: dissolving 1.14g of zinc nitrate hexahydrate in 10g of DMF at room temperature to obtain a solution C, wherein the mass concentration of the zinc nitrate hexahydrate is 11.4%; dissolving 2g of terephthalic acid in 35g of DMF to obtain a solution D, wherein the mass concentration of the terephthalic acid is 5.7%;
step five: placing the carbon fiber II in the third step into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step six: after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step seven: and pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting in an oil bath environment at the temperature of 140 ℃ for 30h, separating the fiber loaded with the MOF-5 crystal by a vacuum filtration method after the reaction is finished, cleaning the fiber loaded with the MOF-5 crystal for a plurality of times by using DMF (dimethyl formamide), drying for later use, and freeze drying (the drying temperature is-65 ℃, the drying time is 50h, and the vacuum degree in the drying process is 20 Pa). Obtaining carbon fiber III;
step eight: carrying out defibering on the carbon fiber III, the aramid fiber and the pulp fiber loaded with the MOF-5 crystal obtained in the seventh step to prepare a fiber mixed solution, wherein the mass ratio of the carbon fiber III to the aramid fiber to the pulp fiber to the filler is 1.2: 1.2: 1.3: 2.8, the sum of the mass percentages is 100 percent. Adding a filler comprising barium sulfate, graphite, aluminum oxide and talcum powder, preparing a wet sample sheet by using the principle of vacuum filtration and a pulping and papermaking mode, and drying the wet sample sheet in an oven at the temperature of 75 ℃ for 2 hours to obtain a dry sample sheet for later use;
step nine: and (5) dipping the dry sample obtained in the step eight in modified phenolic resin, wherein the dipping concentration is 25%, drying at room temperature after completion, and carrying out hot-pressing curing treatment, wherein the hot-pressing temperature is 140 ℃, the curing time is 5min, and the pressure is 15 Pa. Thereby obtaining the MOF-5/dopamine double-effect reinforced paper-based friction material.
Example 4
The method comprises the following steps: soaking 15g of carbon fiber in acetone for 24 hours, removing a sizing agent and other impurities on the surface of the fiber, washing the fiber for 5 times by using deionized water after the completion, drying the fiber in an oven at the temperature of 100 ℃ for 24 hours, and drying the fiber to obtain carbon fiber I with a clean surface;
step two: dissolving 1.2g of Tris (hydroxymethyl) aminomethane (Tris buffer) in 0.97L of deionized water at room temperature, performing magnetic stirring to obtain a solution A, dissolving 2.0g of dopamine in 0.03L of deionized water, and performing ultrasonic dispersion to obtain a solution B;
step three: adjusting the pH value of the solution A to 8.5 by using hydrochloric acid, pouring the solution B into the solution A to fully mix the solution B, wherein the rotation number of magnetic stirring is 1300r during the process of magnetic continuous stirring. Placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, and drying in a drying oven at 105 ℃ for 12 hours after the reaction is finished to obtain carbon fiber II for later use;
step four: dissolving 1.34g of zinc nitrate hexahydrate in 12g of DMF at room temperature to obtain a solution C, wherein the mass concentration of the zinc nitrate hexahydrate is 11.2%; respectively dissolving 3.0g of terephthalic acid in 40g of DMF to obtain a solution D, wherein the mass concentration of the terephthalic acid is 7.5%;
step five: placing the carbon fiber II in the third step into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step six: after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step seven: and pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting in an oil bath environment at the temperature of 120 ℃ for 30h, separating the fiber loaded with the MOF-5 crystal by a vacuum filtration method after the reaction is finished, cleaning the fiber loaded with the MOF-5 crystal for a plurality of times by using DMF (dimethyl formamide), and drying for later use by using an oven (the drying temperature is 105 ℃ and the drying time is 24 h). Obtaining carbon fiber III;
step eight: carrying out defibering on the carbon fiber III, the aramid fiber and the pulp fiber loaded with the MOF-5 crystal obtained in the seventh step to prepare a fiber mixed solution, wherein the mass ratio of the carbon fiber III to the aramid fiber to the pulp fiber to the filler is 1.2: 1.0: 1.3: 3.0, wherein the sum of the mass percentages is 100%. Adding a filler comprising barium sulfate, graphite, aluminum oxide and talcum powder, preparing a wet sample sheet by using the principle of vacuum filtration and a pulping and papermaking mode, and drying the wet sample sheet in an oven at the temperature of 75 ℃ for 4 hours to obtain a dry sample sheet for later use;
step nine: and (5) dipping the dry sample obtained in the step eight in modified phenolic resin, wherein the dipping concentration is 20%, drying at room temperature after completion, and carrying out hot-pressing curing treatment, wherein the hot-pressing temperature is 150 ℃, the curing time is 5min, and the pressure is 15 Pa. Thereby obtaining the MOF-5/dopamine double-effect reinforced paper-based friction material.
Example 5
The method comprises the following steps: soaking 15g of carbon fiber in acetone for 20h, removing a sizing agent and other impurities on the surface of the fiber, washing for 3 times by using deionized water after the completion, drying in an oven at the temperature of 130 ℃ for 24h, and drying to obtain carbon fiber I with a clean surface;
step two: dissolving 1.5g of Tris (hydroxymethyl) aminomethane (Tris buffer) in 0.97L of deionized water at room temperature, performing magnetic stirring to obtain a solution A, dissolving 2.2g of dopamine in 0.03L of deionized water, and performing ultrasonic dispersion to obtain a solution B;
step three: adjusting the pH value of the solution A to 8.5 by using hydrochloric acid, pouring the solution B into the solution A to fully mix the solution B when the magnetic stirring revolution is 1400r during the magnetic continuous stirring process. Placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, and drying in a drying oven at 120 ℃ for 24 hours after the reaction is finished to obtain carbon fiber II for later use;
step four: dissolving 1.04g of zinc nitrate hexahydrate in 12g of DMF at room temperature to obtain a solution C, wherein the mass concentration of the zinc nitrate hexahydrate is 8.7%; dissolving 3.5g of terephthalic acid in 40g of DMF to obtain a solution D, wherein the mass concentration of the terephthalic acid is 8.8%;
step five: placing the carbon fiber II in the third step into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step six: after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step seven: and pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting in an oil bath environment at the temperature of 140 ℃ for 48h, separating the fiber loaded with the MOF-5 crystal by a vacuum filtration method after the reaction is finished, cleaning the fiber loaded with the MOF-5 crystal for a plurality of times by using DMF (dimethyl formamide), and drying for later use by using an oven (the drying temperature is 70 ℃ and the drying time is 12 h). Obtaining carbon fiber III;
step eight: carrying out defibering on the carbon fiber III, the aramid fiber and the pulp fiber loaded with the MOF-5 crystal obtained in the seventh step to prepare a fiber mixed solution, wherein the mass ratio of the carbon fiber III to the aramid fiber to the pulp fiber to the filler is 1.4: 1.2: 1.5: 3.0, wherein the sum of the mass percentages is 100%. Adding fillers including chromite, fluorite powder and talcum powder, preparing a wet sample sheet by a vacuum filtration principle and a pulping and papermaking mode, and drying the wet sample sheet in an oven at the temperature of 75 ℃ for 4 hours to obtain a dry sample sheet for later use;
step nine: and (5) soaking the dry sample obtained in the step eight in modified phenolic resin, wherein the soaking concentration is 30%, drying at room temperature after completion, and performing hot-pressing curing treatment, wherein the hot-pressing temperature is 150 ℃, the curing time is 10min, and the pressure is 5 Pa. Thereby obtaining the MOF-5/dopamine double-effect reinforced paper-based friction material.
Example 6
The method comprises the following steps: soaking 15g of carbon fiber in acetone for 30h, removing a sizing agent and other impurities on the surface of the fiber, washing the fiber for 5 times by using deionized water after the completion, drying the fiber in an oven at the temperature of 130 ℃ for 24h, and drying the fiber to obtain carbon fiber I with a clean surface;
step two: dissolving 1.5g of Tris (hydroxymethyl) aminomethane (Tris buffer) in 1.45L of deionized water at room temperature, performing magnetic stirring to obtain a solution A, dissolving 2.2g of dopamine in 0.05L of deionized water, and performing ultrasonic dispersion to obtain a solution B;
step three: adjusting the pH value of the solution A to 9 by adopting hydrochloric acid, pouring the solution B into the solution A to be fully mixed when the magnetic stirring revolution is 1500r in the process of magnetic continuous stirring. Placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, and drying in a drying oven at 120 ℃ for 24 hours after the reaction is finished to obtain carbon fiber II for later use;
step four: dissolving 1.04g of zinc nitrate hexahydrate in 11g of DMF at room temperature to obtain a solution C, wherein the mass concentration of the zinc nitrate hexahydrate is 9.5%; respectively dissolving 3.0g of terephthalic acid in 40g of deionized water to obtain a solution D, wherein the mass concentration of the terephthalic acid is 7.5%;
step five: placing the carbon fiber II in the third step into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step six: after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step seven: and pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting in an oil bath environment at the temperature of 130 ℃ for 48h, separating the fiber loaded with the MOF-5 crystal by a vacuum filtration method after the reaction is finished, cleaning the fiber loaded with the MOF-5 crystal for a plurality of times by using DMF (dimethyl formamide), and drying for later use, wherein freeze drying can be adopted (the drying temperature is-60 ℃, the drying time is 50h, and the vacuum degree in the drying process is 22 Pa). Obtaining carbon fiber III;
step eight: carrying out defibering on the carbon fiber III, the aramid fiber and the pulp fiber loaded with the MOF-5 crystal obtained in the seventh step to prepare a fiber mixed solution, wherein the mass ratio of the carbon fiber III to the aramid fiber to the pulp fiber to the filler is 1.2: 1.0: 1.3: 3.2, the sum of the mass percentages is 100 percent. Adding fillers including chromite, fluorite powder and talcum powder, preparing a wet sample sheet by a vacuum filtration principle and a pulping and papermaking mode, and drying the wet sample sheet in an oven at the temperature of 80 ℃ for 4 hours to obtain a dry sample sheet for later use;
step nine: and (5) dipping the dry sample obtained in the step eight in modified phenolic resin, wherein the dipping concentration is 20%, drying at room temperature after completion, and carrying out hot-pressing curing treatment, wherein the hot-pressing temperature is 140 ℃, the curing time is 3min, and the pressure is 10 Pa. Thereby obtaining the MOF-5/dopamine double-effect reinforced paper-based friction material.
FIG. 1 is a schematic diagram of a MOF-5/dopamine double-effect modified carbon fiber mechanism. The original carbon fiber has a smooth surface, the chemical inertness of the fiber is strong, the fiber is difficult to form effective combination with a resin matrix, and the problems of fiber falling, matrix debonding and the like are easy to occur in the actual use environment of high temperature and high pressure, so that the friction performance of the material is reduced. Through MOF-5/dopamine double-effect enhancement, firstly, hydrogen bonds or pi-pi bonding can be induced between carbon fibers and a resin matrix by the presence of MOF-5/dopamine, and the flexible dopamine film provides a plurality of growth sites for MOF-5, so that the compatibility of the fibers/the matrix is further promoted. Meanwhile, a large number of MOF-5 bulges with high specific surface area are beneficial to increasing the effective contact area and acting as anchor points, so that the mechanical interlocking with the matrix is further enhanced. In addition, the modified carbon fiber has rich active groups and open metal sites in the middle area, so that the modified carbon fiber can form effective chemical bonds with the matrix. In addition, MOF-5 can act as a three-dimensional armor on the fiber, at-COOH, -OH and Zn2+、Zr4+Chemical and non-chemical bond interactions are generated between the two. Finally, the effective interface combination of the carbon fibers and the resin matrix is enhanced through the double effects of mechanical interlocking and chemical bonding, and the aim of improving the dynamic friction coefficient and the wear rate of the paper-based friction material is fulfilled. FIG. 2 is a comparison of the micro-morphology of the virgin carbon fiber of example 1 and the MOF-5/dopamine dual effect modified carbon fiber of example 3. As can be seen from fig. 2-a, the unmodified carbon fiber has a smooth surface. As is evident from FIG. 2-b, the surface of the carbon fiber which is subjected to MOF-5/dopamine double-effect modification is wrapped by a dopamine film and MOF-5 crystal double layers.
FIG. 3 is the cross-sectional profile of the white sample in example 1 and the MOF-5/dopamine double effect enhanced sample in example 3 after the stretching experiment. As can be seen from fig. 3a and b: a blank paper-based friction material sample is subjected to tensile test experiments, and phenomena such as extraction of a large amount of unmodified carbon fibers, fiber fracture, matrix hole defects and the like appear on a Z-direction section, mainly due to the fact that smooth carbon fibers and a resin matrix are poor in interface bonding, and when the blank paper-based friction material sample is stretched by external force, relative sliding between the fibers and the matrix is easy to generate, and the internal structure of a composite material is damaged. Fig. 3c and d show that the cross-sectional morphology of the MOF-5/dopamine double-effect reinforced sample is smoother after being stretched by an external force, the modified carbon fibers are fixed in the matrix under the double-effect adhesion action of the MOFs and the dopamine, and the interfacial bonding performance of the modified fibers and the resin matrix is remarkably improved under the synergistic action of mechanical interlocking and chemical coupling, so that a reinforced structure with gradient modulus is formed, and stress transfer is facilitated, thereby forming a stable middle area, further reducing stress concentration, and enhancing the capability of the paper-based friction material for resisting the external force.
Table 1 shows the dynamic friction coefficient of the paper-based friction material tested in examples 1-6 under the conditions of brake pressure of 0.5MPa and spindle rotation speed of 2000 r/min. As is evident from the figure: the kinetic coefficient of friction of the MOF-5/dopamine dual enhanced paper-based friction material (example 3) exhibited an upward trend, rising from 0.1068 to 0.1279, with an increase of 19.76%, compared to the blank sample in example 1. After the carbon fibers are modified by the MOF-5 and the dopamine, the dynamic friction coefficient of the paper-based friction material is greatly improved, which is mainly attributed to the fact that an MOF-5 crystal layer grows in situ to form a micro-nano scale protruding structure, the roughness of the surface of the material is obviously improved, and the improvement of the roughness causes the friction pair and a sample to form closer contact and stronger mechanical interlocking, so that larger friction torque is needed to overcome the mechanical engagement, and the dynamic friction coefficient is increased.
TABLE 1 kinetic Friction coefficient of samples before and after MOF-5/dopamine modification
Sample type Coefficient of dynamic friction Increase (%)
Example 1 0.1068 \
Example 2 0.1234 13.45
Example 3 0.1279 19.76
Example 4 0.1236 15.73
Example 5 0.1233 15.45
Example 6 0.1211 13.39
Table 2 shows the wear rates of examples 1 to 6 measured under the conditions of a brake pressure of 0.5MPa, a spindle rotation speed of 2000r/min and a number of times of braking of 200. As is evident from the figure: the wear rate of the MOF-5/dopamine dual enhanced paper-based friction material (example 3) exhibited a decreasing trend from 3.55X 10 as compared to the blank sample of example 1-8cm3·J-1Down to 3.00X 10-8cm3·J-1The amplitude reduction is 15.49%, mainly because the MOF-5 crystal layer and the dopamine film layer are combined with the resin matrix interface to form a stable middle area, the fibers are prevented from being pulled out and debonded from the matrix, and meanwhile, the double-layer structure is beneficial to transferring external stress, reduces a stress concentration area and improves the stress damage resistance of the composite material. Based on the effect of mechanical interlocking and chemical coupling, the interlayer bonding in the material is improved, and the paper-based friction material is obviously improvedThe wear resistance of the material.
TABLE 2 wear rates of samples before and after MOF-5/dopamine modification
Figure BDA0003341547080000171
Figure BDA0003341547080000181

Claims (10)

1. An MOF-5/dopamine double-effect reinforced paper-based friction material comprises carbon fibers, aramid fibers, paper pulp fibers and a filler; the method is characterized in that the carbon fiber is subjected to double modification by MOF-5 and dopamine, and the surface of the carbon fiber has active functional groups which become reactive active sites for MOF-5 crystal growth; the MOF-5 grows on the surface of the carbon fiber in situ, and forms double-effect modified carbon fiber with dopamine, mechanical interlocking occurs between the reinforced carbon fiber and a resin matrix, effective chemical coupling is formed between the reinforced carbon fiber and the resin matrix, and the compatibility of the fiber and the matrix interface and interlayer combination are realized, so that the dynamic friction coefficient is improved by 19.76%; the wear rate is reduced by 15.49%; the mass ratio of the modified carbon fiber, the aramid fiber, the paper pulp fiber and the filler is 1.0-1.4: 1.3-1.6: 2.5-3.0, and the sum of the mass percentages is 100%.
2. The MOF-5/dopamine double effect enhanced paper-based friction material according to claim 1, characterized in that: the filler includes, but is not limited to, barium sulfate, graphite, alumina, chromite, fluorite powder, montmorillonite or talc.
3. A method for preparing the MOF-5/dopamine double effect reinforced paper based friction material of claim 1 or 2, characterized by the following steps:
step 1, carrying out double modification on carbon fibers:
step 1), soaking and cleaning carbon fibers with acetone, removing sizing agent and other impurities on the surfaces of the fibers, and drying to obtain carbon fibers I with clean surfaces;
step 2), dissolving Tris (hydroxymethyl) aminomethane buffer solution in deionized water at room temperature, performing magnetic stirring to obtain solution A, dissolving dopamine in deionized water, and performing ultrasonic dispersion to obtain solution B;
the mass concentration of the dopamine in the solution B is 1.8-2.4%;
step 3), adjusting the pH value of the solution A to 8-9 by adopting acid, and pouring the solution B into the solution A in the process of magnetic continuous stirring to fully mix the solution A; placing the carbon fiber I obtained in the step one in the mixed solution, stirring at normal temperature, and drying for later use after the reaction is finished to obtain carbon fiber II;
step 4), dissolving zinc nitrate hexahydrate in N, N-dimethylformamide DMF at room temperature to obtain a solution C, and dissolving terephthalic acid in DMF to obtain a solution D;
the mass concentration of zinc nitrate hexahydrate in the solution C is 8.4-14.8%;
the mass concentration of the terephthalic acid in the solution D is 3.7-11.6%;
step 5), placing the carbon fiber II in the step three into the solution C, continuously stirring and fully mixing to ensure that Zn is formed2+Forming Zn-O bonds on the carbon fibers through the reaction of chemical bonds and free hydroxyl groups on a dopamine active layer on the surface of the carbon fibers II, thereby obtaining a fiber suspension I;
step 6), after the fiber suspension I is uniformly stirred, immediately pouring the solution D into the fiber suspension I, and continuously stirring to obtain a fiber suspension II;
step 7), pouring the suspension II into a polytetrafluoroethylene reaction kettle, reacting for 24-48 h in an oil bath at 120-150 ℃, separating fibers loaded with MOF-5 crystals by a vacuum filtration method after the reaction is finished, cleaning the fibers loaded with the MOF-5 crystals for a plurality of times by using DMF, and drying to obtain an MOF-5/dopamine modified carbon fiber III;
step 2: carrying out defibering on the MOF-5/dopamine modified carbon fiber III, aramid fiber and pulp fiber to prepare a fiber mixed solution, adding a filler, preparing a wet sample sheet by a vacuum filtration principle and a pulping and papermaking mode, and drying the wet sample sheet in an oven;
the mass ratio of the carbon fiber III to the aramid fiber to the paper pulp fiber to the filler is 1.0-1.4: 1.3-1.6: 2.5-3.0;
and step 3: and (3) dipping the dry sample obtained in the step (2) in modified phenolic resin, and drying at room temperature after completion, wherein the hot-pressing curing temperature is 130-150 ℃, the curing time is 3-10 min, and the curing pressure is 5-15 Pa, so that the hot-pressing curing treatment is completed, and the MOF-5/dopamine double-effect reinforced paper-based friction material is obtained.
4. The method of claim 3, wherein: the step 1) is to put the carbon fiber into an acetone solution to be soaked for 12-48 h, wherein the drying temperature is 80-150 ℃, and the drying time is 12-24 h.
5. The method of claim 3, wherein: the mass concentration of the Tris buffer solution in the solution A in the step 2) is 1.0-2.0%.
6. The method of claim 3, wherein: the acid regulating solution of step 3) includes, but is not limited to, hydrochloric acid, acetic acid or sulfuric acid.
7. The method of claim 3, wherein: the magnetic stirring revolution in the step 3) is 1000-1500r, the drying temperature is 80-150 ℃, and the drying time is 12-24 h.
8. The method of claim 3, wherein: the drying mode of the carbon fiber III in the step 7) comprises freeze drying, oven drying or normal temperature drying; when freeze-dried: the drying temperature is-45 to-65 ℃, the drying time is 48 to 56 hours, and the vacuum degree in the drying process is 15 to 25 Pa; when the oven is dry: the drying temperature is 70-105 ℃, and the drying time is 12-24 h.
9. The method of claim 3, wherein: and (3) drying the oven in the step (2) at the drying temperature of 50-75 ℃ for 1-4 h.
10. The method of claim 3, wherein: in the step 3, the impregnation concentration of the modified phenolic resin is 10-30%.
CN202111309803.1A 2021-11-07 2021-11-07 MOF-5/dopamine double-effect enhanced paper-based friction material and preparation method thereof Pending CN114086424A (en)

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US20070137818A1 (en) * 2005-12-21 2007-06-21 Levit Mikhail R Para-aramid pulp including meta-aramid fibrids and processes of making same
CN109608822A (en) * 2018-12-03 2019-04-12 陕西科技大学 A kind of lossless modified carbon fiber reinforced resin base Wet-type friction material of MOF-5 and preparation method thereof
CN113445360A (en) * 2021-06-25 2021-09-28 西北工业大学 Rigid-flexible ZIF-8/dopamine cooperative enhancement type paper-based friction material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070137818A1 (en) * 2005-12-21 2007-06-21 Levit Mikhail R Para-aramid pulp including meta-aramid fibrids and processes of making same
CN109608822A (en) * 2018-12-03 2019-04-12 陕西科技大学 A kind of lossless modified carbon fiber reinforced resin base Wet-type friction material of MOF-5 and preparation method thereof
CN113445360A (en) * 2021-06-25 2021-09-28 西北工业大学 Rigid-flexible ZIF-8/dopamine cooperative enhancement type paper-based friction material and preparation method thereof

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