CN114752868B - A copper-coated basalt fiber reinforced copper matrix composite material and its preparation method and application - Google Patents
A copper-coated basalt fiber reinforced copper matrix composite material and its preparation method and application Download PDFInfo
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- CN114752868B CN114752868B CN202210411812.XA CN202210411812A CN114752868B CN 114752868 B CN114752868 B CN 114752868B CN 202210411812 A CN202210411812 A CN 202210411812A CN 114752868 B CN114752868 B CN 114752868B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 123
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 115
- 239000010949 copper Substances 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011159 matrix material Substances 0.000 title claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007788 roughening Methods 0.000 claims abstract description 8
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims description 70
- 238000010438 heat treatment Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 5
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 5
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 4
- 239000002783 friction material Substances 0.000 claims description 3
- 230000001235 sensitizing effect Effects 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 238000002156 mixing Methods 0.000 description 17
- 238000003825 pressing Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- 238000004321 preservation Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 9
- 206010070834 Sensitisation Diseases 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000008313 sensitization Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 230000001976 improved effect Effects 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 206010003549 asthenia Diseases 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- -1 whiskers Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
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- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
- C23C18/1865—Heat
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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Abstract
本发明公开了一种镀铜玄武岩纤维增强铜基复合材料的制备方法，包括以下步骤：S1.将玄武岩纤维进行预热处理，然后采用氢氟酸进行粗化处理；S2.将粗化处理的玄武岩纤维置于镀铜溶液中进行化学镀铜处理；S3.将镀铜后的玄武岩纤维与铜粉混合后压制成型，经放电等离子烧结制备得到镀铜玄武岩纤维增强铜基复合材料，其中，所述铜基复合材料中镀铜玄武岩纤维的含量为1～3wt.％。本发明还提供了由所述方法制备的镀铜玄武岩纤维增强铜基复合材料及其应用。本发明的镀铜玄武岩纤维增强铜基复合材料的制备方法，通过化学镀铜的方法在玄武岩纤维表面形成镀铜层，改善了玄武岩纤维与铜的界面结合，提高了铜基复合材料的力学性能。
The invention discloses a method for preparing a copper-plated basalt fiber reinforced copper-based composite material, which comprises the following steps: S1. preheating the basalt fiber, and then roughening it with hydrofluoric acid; S2. roughening the roughened The basalt fiber is placed in the copper plating solution for electroless copper plating; S3. The copper-plated basalt fiber is mixed with copper powder and then pressed into shape, and the copper-coated basalt fiber-reinforced copper matrix composite material is prepared by spark plasma sintering, wherein, the The content of the copper-coated basalt fiber in the copper-based composite material is 1-3 wt.%. The invention also provides the copper-coated basalt fiber-reinforced copper matrix composite material prepared by the method and its application. The preparation method of copper-plated basalt fiber-reinforced copper-based composite material of the present invention forms a copper-coated layer on the surface of basalt fiber by chemical copper plating, improves the interface bonding between basalt fiber and copper, and improves the mechanical properties of copper-based composite material .
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a copper-plated basalt fiber reinforced copper-based composite material, and a preparation method and application thereof.
Background
Copper has excellent electric conduction, heat conduction and processing performance, and is widely applied to the fields of aerospace, ocean engineering, electronics, automobiles and the like. Pure copper, however, has a relatively low strength, which has led to great limitations in the use of copper in certain fields. The second phase with higher strength, such as particles, whiskers, fibers and the like, is introduced into the copper matrix, so that the copper-based composite material is prepared, the strength of the copper material is improved, the advantages of each component are fully exerted, and therefore, the copper-based composite material is widely focused and studied.
Basalt fiber is used as a novel environment-friendly material, and has the advantages of wide sources, abundant resources and excellent performance. In particular, basalt fibers have a higher cost performance than other fibers. Therefore, basalt fibers are introduced into a copper matrix as a reinforcing phase, and the defect of low strength of the copper material is expected to be overcome. For example, chinese patent publication No. CN106119746a (publication date: 2016, 11, 16) discloses a corrosion-resistant basalt fiber reinforced copper-based alloy composite material, which is obtained by mixing basalt fibers with copper-based alloy powder, pressing the mixture into a compact at room temperature, and then sintering the compact at 1240-1300 ℃. The composite material has high chemical stability, corrosion resistance, excellent erosion resistance and stress corrosion cracking resistance, high hardness and breaking strength exceeding 1000MPa.
However, in order to fully exert the reinforcing effect of basalt fiber in copper-based composite materials, the following two problems have yet to be solved. On the one hand, basalt fibers belong to nonmetallic materials, and have the problem of weaker interface combination with copper; on the other hand, the sintering preparation temperature of the copper-based composite material is higher, and the mechanical properties of the basalt fiber can be seriously damaged by high-temperature heat cycle.
Chinese patent publication No. CN110791718A (publication No. 2020, 2, 14) discloses a basalt fiber reinforced copper-based powder metallurgy material, which is prepared by coating basalt fiber with alumina, then attaching copper oxide or titanium, and cold-pressing sintering. The modification of the basalt fiber surface realizes the change of the interface reaction system of the basalt fiber and the metal matrix, improves the interface bonding condition, improves the brittleness of the composite material and improves the mechanical property of the copper-based material. But the sintering temperature is as high as 800-1000 ℃, the heat preservation time is as long as 3-4 hours, and the sintering temperature and the heat preservation time can cause obvious loss of strength of basalt fibers in the sintering process, which is not beneficial to the improvement of strength of copper-based composite materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a copper-plated basalt fiber reinforced copper-based composite material, which comprises the steps of forming a copper plating layer on the surface of basalt fiber by an electroless copper plating method, so that the interface combination of basalt fiber and copper is improved; on the other hand, by adopting electric field to assist sintering, the sintering temperature is reduced, the heat preservation time is shortened, the damage of high temperature heat cycle to the mechanical property of basalt fiber is reduced, and the mechanical property of the copper-based composite material is further improved.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a copper-plated basalt fiber reinforced copper-based composite material, which comprises the following steps:
s1, preheating basalt fibers, and then coarsening with hydrofluoric acid;
s2, placing the coarsened basalt fiber into a copper plating solution for electroless copper plating treatment;
s3, mixing the basalt fiber subjected to copper plating with copper powder, then pressing and forming, and preparing the copper-plated basalt fiber reinforced copper-based composite material through spark plasma sintering, wherein the content of the copper-plated basalt fiber in the copper-based composite material is 1-3 wt.%.
Further, in step S1, the diameter of the basalt fiber is 8-12 μm.
In the invention, the original basalt fiber is firstly subjected to preheating treatment before copper plating, so that the organic coating on the surface of the basalt fiber can be removed, and the subsequent electroless copper plating is facilitated.
Further, in step S1, the heating temperature of the preheating treatment is 350-450 ℃, the heat preservation time is 10-30 min, and the heating vacuum degree is higher than 5 multiplied by 10 -3 Pa. If the heat treatment is performed in air, defects are easily formed on the surface of the basalt fiber, and oxidation of ferrous ions in the basalt fiber is caused, resulting in a significant decrease in fiber strength. According to the invention, the formation of basalt fiber surface defects can be reduced by carrying out heat treatment in vacuum, and the crystallization of basalt can be promoted by vacuum, so that the high temperature resistance of the basalt is improved, and the strength reduction caused in the sintering preparation process of the composite material is reduced. And, in the basalt fiber heat treatment process, the higher the temperature and the longer the time, the more the fiber strength is reduced. The invention can reduce the decrease of the fiber strength in the subsequent sintering heat treatment process by controlling the heat treatment temperature to be 350-450 ℃ and the heat preservation time to be 10-30 min.
Further, in step S1, the roughening treatment is: and (3) soaking the basalt fiber after the preheating treatment in an HF solution with the weight of 2-8% for 5-10 min, and then cleaning the basalt fiber by adopting absolute ethyl alcohol. The roughening treatment can increase the surface roughness of the basalt fiber, so that the bonding capability of the basalt fiber and the copper plating layer is improved.
Further, in step S2, the electroless copper plating process includes:
putting basalt fiber into a sensitization solution for ultrasonic vibration for 30-60 min, wherein the sensitization solution comprises the following formula: snCl 2 20-30 g/L,37wt.% HCl 40-60 mL/L, and deionized water as the rest;
then, putting the sensitized basalt fiber into an activating solution, carrying out ultrasonic vibration for 30-60 min, and carrying out vacuum drying after ethanol cleaning; wherein said at least one ofThe formula of the activating solution is as follows: pdCl 2 0.5-1 g/L,37wt.% HCl 5-10 mL/L, and deionized water as the rest;
finally, placing the basalt fiber subjected to activation treatment in an electroless copper plating solution, heating the copper plating solution to 35-45 ℃, continuously stirring for 3-5 min, filtering, cleaning for multiple times, and drying to obtain the copper plating basalt fiber; wherein, the formula of the electroless copper plating solution is as follows: 20-30 g/L of disodium ethylenediamine tetraacetate, 20-25 g/L of cupric sulfate pentahydrate, 10-14 g/L of sodium hydroxide, 15-20 mL/L of formaldehyde solution, 20-30 g/L of potassium sodium tartrate and the balance of deionized water.
Further, in step S3, the copper powder is micro copper powder or nano copper powder.
Further, in the step S3, the pressure of the compression molding is 60-80 MPa, and the pressure maintaining time is 15-20 min.
Compared with the traditional hot-pressing sintering method, the invention adopts high-vacuum and rapid-heating electric field assisted sintering, has high temperature rising speed and short heat preservation time, and can obviously reduce the strength loss of basalt fibers in the sintering process. Further, in the step S3, the heating speed of the spark plasma sintering is 100-200 ℃/min, the sintering temperature is 550-750 ℃, the heat preservation time is 5-10 min, and the sintering pressure is 50-80 MPa.
Further, in the present invention, the degree of vacuum during sintering is higher than 5×10 -3 Pa. The high vacuum is beneficial to reducing the defects of the fiber surface, promoting the crystallization of basalt, further improving the high temperature resistance and reducing the strength loss in the sintering process. In some solutions in the prior art, the sintering is performed under the protection of an inert atmosphere, but the inert atmosphere can only reach 10 -1 ～10 -2 Pa, and the evacuation can reach a higher vacuum. Therefore, the invention controls the vacuum degree to be higher than 5 multiplied by 10 by vacuumizing -3 Pa, compared with inert atmosphere protection, can better reduce the strength loss of basalt fiber.
In the invention, after sintering is finished, cooling to below 50 ℃ along with the furnace and taking out.
In a second aspect, the invention provides a copper-plated basalt fiber reinforced copper-based composite material prepared by the method.
In a third aspect, the invention provides application of the copper-plated basalt fiber reinforced copper-based composite material in friction materials.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional high-price fibers such as carbon fibers, the basalt fibers used in the invention have the advantages of wide sources, abundant resources, small gap between the performance and the high-performance fibers such as carbon fibers, and remarkably reduced cost.
2. The interface combination between basalt fiber and copper is improved after the basalt fiber is roughened by hydrofluoric acid and treated by electroless copper plating.
3. The crystallization of the basalt fiber is promoted by the preheating treatment, so that the high temperature resistance of the basalt fiber is improved. Meanwhile, the electric field assisted sintering with high vacuum and rapid heating is adopted, so that the strength loss of basalt fibers in the sintering process is reduced.
4. The basalt fiber reinforced copper-based composite material has wide application prospect in the field of friction materials requiring high friction stability and high wear resistance.
Drawings
FIG. 1 is an SEM topography of an original basalt fiber;
FIG. 2 is an SEM topography of the copper-plated basalt fiber prepared in example 1;
FIG. 3 is a photograph of the microstructure of a basalt fiber reinforced copper matrix composite;
FIG. 4 shows fracture morphology of the copper-based composite prepared in example 1 and comparative example 3.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Example 1
The embodiment discloses a preparation method of a copper-plated basalt fiber reinforced copper-based composite material, which comprises the following steps:
(1) Placing the original basalt fiber into a vacuum furnace, wherein the vacuum degree is 1-3×10 -3 Pa, heating to 400 ℃, and preserving heat for 20min. And (3) turning off the power supply, taking the basalt fiber out of the furnace when the temperature in the furnace is reduced to below 50 ℃, and obtaining the basalt fiber after the preheating treatment. The original morphology of basalt fiber is shown in fig. 1.
(2) And (3) immersing the basalt fiber obtained in the step (1) in an HF solution of 4wt.% for 10min, and carrying out surface roughening treatment.
(3) And (3) putting the basalt fiber obtained in the step (2) into a sensitization solution, carrying out ultrasonic vibration for 30min, then putting into an activation solution, carrying out ultrasonic vibration for 30min, and washing and drying with alcohol for many times. The formulation of the sensitization solution is: snCl 2 20g/L;37wt.% HCl,40mL/L; the rest is deionized water. The ratio of the activating solution is as follows: pdCl 2 0.5g/L;37wt.% HCl,5mL/L; the rest is deionized water.
(4) And (3) putting the sensitized and activated basalt fiber into a copper plating solution, heating the copper plating solution to 40 ℃, continuously stirring for 5min, filtering, cleaning for multiple times, and drying to obtain the copper plating basalt fiber. The formulation of the electroless copper plating solution is: disodium ethylenediamine tetraacetate, 28g/L; copper sulfate pentahydrate, 20g/L; 12g/L of sodium hydroxide; formaldehyde solution, 15mL/L; potassium sodium tartrate, 20g/L; the balance of deionized water.
The microscopic morphology of the copper plated basalt fiber is shown in fig. 2. From the figure, basalt fibers are completely covered by a copper plating layer, and the copper plating layer is uniform and compact in thickness and free of microscopic defects.
(5) 3g of copper-plated basalt fiber and 97g of electrolytic copper powder are taken to be placed into a mixing tank, the mixing tank is arranged on a mixer to mix materials for 4 hours, and the rotation speed of the mixer is 150r/min, so that composite powder is obtained.
(6) Putting the composite powder into a stainless steel die with the inner diameter of phi 40mm, and cold-pressing and molding under a hydraulic press. The cold pressing pressure is 60MPa, and the pressure maintaining time is 20min, so that a sintered blank is obtained.
(7) And (3) filling the sample subjected to cold press molding into a graphite mold with the inner diameter of phi 40mm, and sintering in a discharge plasma sintering furnace. The sintering vacuum degree is 1-3 multiplied by 10 -3 Pa, the sintering temperature is 650 ℃, the heating speed is 100 ℃/min, the heat preservation time is 5min, the sintering pressure is 60MPa, and the copper-plated basalt fiber reinforced copper-based composite material is obtained after cooling to below 50 ℃ along with a furnace and taking out after sintering.
The microstructure of the composite after sintering is shown in fig. 3. As can be seen from the figure, basalt fibers are uniformly distributed, and no agglomeration phenomenon exists. The composite material has compact structure and no defects such as air holes, cracks and the like.
Example 2
The embodiment discloses a preparation method of a copper-plated basalt fiber reinforced copper-based composite material, which comprises the following steps:
(1) Placing the original basalt fiber into a vacuum furnace, wherein the vacuum degree is 1-3×10 -3 Pa, heating to 400 ℃, and preserving heat for 20min. And (3) turning off the power supply, taking the basalt fiber out of the furnace when the temperature in the furnace is reduced to below 50 ℃, and obtaining the basalt fiber after the preheating treatment.
(2) And (3) immersing the basalt fiber obtained in the step (1) in an HF solution of 4wt.% for 10min, and carrying out surface roughening treatment.
(3) And (3) putting the basalt fiber obtained in the step (2) into a sensitization solution, carrying out ultrasonic vibration for 30min, then putting into an activation solution, carrying out ultrasonic vibration for 30min, and washing and drying with alcohol for many times. The formulation of the sensitization solution is: snCl 2 20g/L;37wt.% HCl,40mL/L; the rest is deionized water. The ratio of the activating solution is as follows: pdCl 2 0.5g/L;37wt.% HCl,5mL/L; the remainder isThe balance of deionized water.
(4) And (3) putting the sensitized and activated basalt fiber into a copper plating solution, heating the copper plating solution to 40 ℃, continuously stirring for 5min, filtering, cleaning for multiple times, and drying to obtain the copper plating basalt fiber. The formulation of the electroless copper plating solution is: disodium ethylenediamine tetraacetate, 28g/L; copper sulfate pentahydrate, 20g/L; 12g/L of sodium hydroxide; formaldehyde solution, 15mL/L; potassium sodium tartrate, 20g/L; the balance of deionized water.
(5) 2g of copper-plated basalt fiber and 98g of electrolytic copper powder are taken to be placed into a mixing tank, the mixing tank is arranged on a mixer to mix materials for 4 hours, and the rotation speed of the mixer is 150r/min, so that composite powder is obtained.
(6) Putting the composite powder into a stainless steel die with the inner diameter of phi 40mm, and cold-pressing and molding under a hydraulic press. The cold pressing pressure is 60MPa, and the pressure maintaining time is 20min, so that a sintered blank is obtained.
(7) And (3) filling the sample subjected to cold press molding into a graphite mold with the inner diameter of phi 40mm, and sintering in a discharge plasma sintering furnace. The sintering vacuum degree is 1-3 multiplied by 10 -3 Pa, the sintering temperature is 650 ℃, the heating speed is 100 ℃/min, the heat preservation time is 5min, the sintering pressure is 60MPa, and the copper-plated basalt fiber reinforced copper-based composite material is obtained after cooling to below 50 ℃ along with a furnace and taking out after sintering.
Example 3
The embodiment discloses a preparation method of a copper-plated basalt fiber reinforced copper-based composite material, which comprises the following steps:
(1) Placing the original basalt fiber into a vacuum furnace, wherein the vacuum degree is 1-3×10 -3 Pa, heating to 400 ℃, and preserving heat for 20min. And (3) turning off the power supply, taking the basalt fiber out of the furnace when the temperature in the furnace is reduced to below 50 ℃, and obtaining the basalt fiber after the preheating treatment.
(2) And (3) immersing the basalt fiber obtained in the step (1) in an HF solution of 4wt.% for 10min, and carrying out surface roughening treatment.
(3) Putting the basalt fiber obtained in the step (2) into a sensitization solution, performing ultrasonic vibration for 30min, then putting into an activation solution, performing ultrasonic vibration for 30min, and performing alcohol treatmentWashing and drying for multiple times. The formulation of the sensitization solution is: snCl 2 20g/L;37wt.% HCl,40mL/L; the rest is deionized water. The ratio of the activating solution is as follows: pdCl 2 0.5g/L;37wt.% HCl,5mL/L; the rest is deionized water.
(4) And (3) putting the sensitized and activated basalt fiber into a copper plating solution, heating the copper plating solution to 40 ℃, continuously stirring for 5min, filtering, cleaning for multiple times, and drying to obtain the copper plating basalt fiber. The formulation of the electroless copper plating solution is: disodium ethylenediamine tetraacetate, 28g/L; copper sulfate pentahydrate, 20g/L; 12g/L of sodium hydroxide; formaldehyde solution, 15mL/L; potassium sodium tartrate, 20g/L; the balance of deionized water.
(5) 2g of copper-plated basalt fiber and 98g of electrolytic copper powder are taken to be placed into a mixing tank, the mixing tank is arranged on a mixer to mix materials for 4 hours, and the rotation speed of the mixer is 150r/min, so that composite powder is obtained.
(6) Putting the composite powder into a stainless steel die with the inner diameter of phi 40mm, and cold-pressing and molding under a hydraulic press. The cold pressing pressure is 60MPa, and the pressure maintaining time is 20min, so that a sintered blank is obtained.
(7) And (3) filling the sample subjected to cold press molding into a graphite mold with the inner diameter of phi 40mm, and sintering in a discharge plasma sintering furnace. The sintering vacuum degree is 1-3 multiplied by 10 -3 Pa, the sintering temperature is 650 ℃, the heating speed is 120 ℃/min, the heat preservation time is 5min, the sintering pressure is 60MPa, and the copper-plated basalt fiber reinforced copper-based composite material is obtained after cooling to below 50 ℃ along with a furnace and taking out after sintering.
Comparative example 1
And (1) putting 3g basalt fiber which is not subjected to the treatment in the steps (1), (2), (3) and (4) in the embodiment 1 and 97g electrolytic copper powder into a mixing tank, and mounting the mixing tank on a mixer to mix for 4 hours, wherein the rotation speed of the mixer is 150r/min, so as to obtain composite powder.
(2) Putting the composite powder into a stainless steel die with the inner diameter of phi 40mm, and cold-pressing and molding under a hydraulic press. The cold pressing pressure is 60MPa, and the pressure maintaining time is 20min, so that a sintered blank is obtained.
(3) Filling the cold-pressed sample into a sample with an inner diameter of phi 40mmIn the graphite mold, sintering is performed in a spark plasma sintering furnace. The sintering vacuum degree is 1-3 multiplied by 10 -3 Pa, the sintering temperature is 650 ℃, the heating speed is 100 ℃/min, the heat preservation time is 5min, the sintering pressure is 60MPa, and the copper-plated basalt fiber reinforced copper-based composite material is obtained after cooling to below 50 ℃ along with a furnace and taking out after sintering.
Comparative example 2
8g basalt fiber treated in the steps (1), (2), (3) and (4) in the embodiment 1 and 97g electrolytic copper powder are put into a mixing tank, the mixing tank is arranged on a mixer for mixing for 4 hours, and the rotation speed of the mixer is 150r/min, so that composite powder is obtained.
(2) Putting the composite powder into a stainless steel die with the inner diameter of phi 40mm, and cold-pressing and molding under a hydraulic press. The cold pressing pressure is 60MPa, and the pressure maintaining time is 20min, so that a sintered blank is obtained.
(3) And (3) filling the sample subjected to cold press molding into a graphite mold with the inner diameter of phi 40mm, and sintering in a discharge plasma sintering furnace. The sintering vacuum degree is 1-3 multiplied by 10 -3 Pa, the sintering temperature is 650 ℃, the heating speed is 100 ℃/min, the heat preservation time is 5min, the sintering pressure is 60MPa, and the copper-plated basalt fiber reinforced copper-based composite material is obtained after cooling to below 50 ℃ along with a furnace and taking out after sintering.
Comparative example 3
And (1) putting 3g basalt fiber treated in the steps (1), (2), (3) and (4) in the embodiment 1 and 97g electrolytic copper powder into a mixing tank, and mounting the mixing tank on a mixer to mix for 4 hours, wherein the rotation speed of the mixer is 150r/min, so as to obtain composite powder.
(2) Putting the composite powder into a stainless steel die with the inner diameter of phi 40mm, and cold-pressing and molding under a hydraulic press. The cold pressing pressure is 60MPa, and the pressure maintaining time is 20min, so that a sintered blank is obtained.
(3) And (3) filling the cold-pressed sample into a graphite mold with the inner diameter of phi 40mm, and sintering in a traditional hot-pressing sintering furnace. The sintering vacuum degree is 1-3 multiplied by 10 -3 Pa, sintering temperature 650 ℃, heating speed 20 ℃/min, heat preservation time 30min, sintering pressure 60MPa, cooling to below 50 ℃ along with a furnace after sintering is finished, and taking outAnd obtaining the copper-plated basalt fiber reinforced copper-based composite material. For traditional hot press sintering, too short a heat preservation time can result in the failure of the sample to sinter dense. Therefore, in order to obtain a density similar to that of example 1, the heat-retaining time of hot press sintering was increased to 30min.
Comparative example 4
And (1) putting 3g basalt fiber treated in the steps (1), (2), (3) and (4) in the embodiment 1 and 97g electrolytic copper powder into a mixing tank, and mounting the mixing tank on a mixer to mix for 4 hours, wherein the rotation speed of the mixer is 150r/min, so as to obtain composite powder.
(2) Putting the composite powder into a stainless steel die with the inner diameter of phi 40mm, and cold-pressing and molding under a hydraulic press. The cold pressing pressure is 60MPa, and the pressure maintaining time is 20min, so that a sintered blank is obtained.
(3) And (3) filling the sample subjected to cold press molding into a graphite mold with the inner diameter of phi 40mm, and sintering in a discharge plasma sintering furnace. The sintering vacuum degree is 1-3 multiplied by 10 -3 Pa, the sintering temperature is 800 ℃, the heating speed is 100 ℃/min, the heat preservation time is 5min, the sintering pressure is 60MPa, and the copper-plated basalt fiber reinforced copper-based composite material is obtained after cooling to below 50 ℃ along with a furnace and taking out after sintering.
Performance testing
The copper-plated basalt fiber-reinforced copper matrix composite materials prepared in examples 1 to 3 and comparative examples 1 to 4 were tested for brinell hardness, tensile strength and wear rate, and the results are shown in table 1.
Table 1 performance tables of copper-based composite materials prepared in examples and comparative examples
| Brinell Hardness (HBW) | Tensile Strength (MPa) | Wear rate (mg/Km) | |
| Example 1 | 43.7 | 297 | 21 |
| Example 2 | 43.1 | 294 | 31 |
| Example 3 | 42.3 | 288 | 36 |
| Comparative example 1 | 33.4 | 208 | 51 |
| Comparative example 2 | 35.6 | 231 | 45 |
| Comparative example 3 | 32.5 | 192 | 54 |
| Comparative example 4 | 30.6 | 177 | 62 |
As can be seen from Table 1, the copper-clad basalt fiber-reinforced copper-based composite materials prepared in examples 1 to 3 have higher Brinell hardness, tensile strength and lower wear rate. The performance data of comparative example 1 and comparative example 1 can show that copper plating on the basalt fiber surface can significantly improve the mechanical and tribological properties of copper-based composite materials. As can be seen from comparative example 1 and comparative example 2, the mass range of the copper-plated basalt fiber should be 1-3%. The performance data of comparative example 1 and comparative example 3 show that basalt fiber reinforced copper matrix composites prepared by conventional hot pressed sintering have poor performance.
Fig. 4 shows fracture morphology of the composite materials obtained in example 1 and comparative example 3 after a tensile test. From the fracture morphology photo, the fiber pulling-out phenomenon exists at the fracture of the composite material prepared by spark plasma sintering, and the fiber strength is proved to be higher. The fracture phenomenon of the fiber exists on the section of the composite material prepared by traditional hot-pressing sintering, which indicates that the strength of the fiber is obviously reduced and the fiber is broken in the stretching process. The reason is that the traditional hot-pressing sintering has low temperature rising speed and long thermal cycle time, and the strength of basalt fiber is greatly reduced. Therefore, in order to maintain the excellent mechanical properties of basalt fibers, the composite material needs to adopt a proper preparation method and preparation process parameters. Comparative example 1 and comparative example 4 further illustrate that the preparation method and process of the copper-plated basalt fiber-reinforced copper-based composite material provided by the invention are more reasonable.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
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