CN110699676A - High-strength high-conductivity metal glass composite material and preparation method thereof - Google Patents
High-strength high-conductivity metal glass composite material and preparation method thereof Download PDFInfo
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- CN110699676A CN110699676A CN201911139237.7A CN201911139237A CN110699676A CN 110699676 A CN110699676 A CN 110699676A CN 201911139237 A CN201911139237 A CN 201911139237A CN 110699676 A CN110699676 A CN 110699676A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 143
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 108
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
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- 239000003381 stabilizer Substances 0.000 claims description 2
- 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 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- B22F1/0003—
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
Abstract
The invention provides a high-strength high-conductivity metal glass composite material and a preparation method thereof, wherein the preparation method comprises the following steps: preparation of Cu50Zr43Al7Powder particles; in the obtained Cu50Zr43Al7Pretreating the powder particles before plating, then carrying out chemical plating, cleaning and drying to obtain the Cu coated with copper50Zr43Al7A metallic glass powder; coating copper with Cu50Zr43Al7The metal glass powder and the copper powder are mixed for spark plasma sintering to obtain the product with high strength and high strengthThe sintering temperature of the metal glass composite material with the conductivity is not more than 503 ℃. By adopting the technical scheme of the invention, the composite powder is prepared by adopting a method of chemically plating copper on specific metal glass powder, so that crystal copper is uniformly and firmly combined with the metal glass powder, and finally mixed with copper powder for sintering to obtain the composite material.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a high-strength high-conductivity metal glass composite material and a preparation method thereof.
Background
Metallic glass, also known as amorphous alloy, refers to an alloy in which the three-dimensional space of atoms is topologically disordered when in a solid state and this state remains relatively stable over a range of temperatures. The amorphous alloy has unique and excellent physical, chemical and mechanical properties due to the unique long-range disordered and short-range ordered structure and no crystal defects such as dislocation, grain boundary and the like. For example, the strength of some cobalt-based amorphous alloys is as high as 6000MPa, which is almost the highest strength of bulk metallic materials; in addition, the zirconium-based amorphous alloy also has high elastic limit (about 2%), high fracture toughness, super plasticity of a supercooled liquid phase region, high hardness, ultrahigh corrosion resistance, wear resistance and fatigue resistance. Since the last 80 s of the century, the development of hundreds of types of bulk amorphous alloy systems has been developed through the last thirty years since bulk amorphous alloys were prepared in La-Al-Ni based alloys by copper mold casting, and the specific alloy components are more. Each alloy system has its own characteristics, both in terms of its glass forming ability and its physical, chemical and mechanical properties.
On the other hand, in all metals, alloys and composite materials, high strength and high conductivity always have contradictory characteristics, and the high-strength and high-conductivity composite material is a composite material with excellent conductivity and heat conductivity and much higher strength than pure copper, and is a functional structural material with excellent comprehensive physical properties and mechanical properties. It has both high strength and good ductility, as well as good electrical and thermal conductivity characteristics. The high-power asynchronous traction motor has wide application in various modern scientific and technological fields, such as an electrical contact of an electrical engineering switch in the electrical communication industry, a collecting ring, an armature and an electrode of a resistance explosion electrode engine, an electrified railway contact wire, a high-power asynchronous traction motor rotor and the like; lead frames for various integrated circuits in the electronics industry; blast furnace tuyeres, continuous casting crystallizers, oxygen lance nozzles which need to be in a high conductivity heat transfer environment, and the like in the metallurgical industry; and vertical boot radiating fins of a divertor of a thermonuclear experiment reactor, high-strength pulse magnetic field conductive materials and the like.
However, in many materials currently used in industry, it is difficult to have both high strength and high conductivity, and although pure metals such as Cu and Ag have high conductivity, their strength is very low, often less than 200 MPa. While increasing its strength, it inevitably results in a sharp decrease in conductivity. Since the last 80 s, with the rapid development of the electronic industry, especially the development of high-intensity magnet technology, a new wave has been developed for the research on a new generation of high-strength high-conductivity materials. A great deal of research and development work is carried out on the materials at home and abroad, so that the materials are rapidly developed. In 2004, Luko et al published a new approach to develop twin strengthening metals in nanometer size to obtain copper with ultra-high strength and high conductivity, the yield strength of which can reach 900MPa and the conductivity of which reaches 97% IACS, but the preparation process is extremely complex and only a film sample can be prepared, so the method is far from industrial application. In recent years, the overall index of the Cu-Cr (Zr) series high-strength high-conductivity alloy OMLC-1 developed by Mitsubishi corporation can reach 621MPa of tensile strength and 82.7 percent of IACS. The Cu-Mg series alloy developed by German railway company (DBAG) is applied to a contact net of an electrified high-speed railway at first, and compared with other alloy elements, the alloy can obtain higher strength and keep better conductive performance without subsequent heat treatment.
At present, the electric contact switch industry is mostly applied to copper beryllium alloy, the tensile strength is more than or equal to 1000MPa, and the electric conductivity is only more than or equal to 18 percent IACS. Although it has excellent combination of strength, hardness, electrical conductivity, thermal conductivity and high temperature stability, beryllium element and its compounds have very high toxicity, so long as one milligram of beryllium dust is in each cubic meter of air, it can cause acute pneumonia-pneumonitis. Considering the damage to the environment and human body in the preparation process, the industry of various countries is always looking for green, environment-friendly, low-cost and excellent-performance materials to replace copper-beryllium alloy.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a high-strength high-conductivity metal glass composite material and a preparation method thereof, which have both high strength and high conductivity.
In contrast, the technical scheme adopted by the invention is as follows:
a preparation method of a metal glass composite material with high strength and high conductivity comprises the following steps:
step S1, preparing Cu50Zr43Al7Powder particles;
step S2, Cu obtained in step S150Zr43Al7Pretreating the powder particles before plating, then carrying out chemical plating, cleaning and drying to obtain the Cu coated with copper50Zr43Al7A metallic glass powder;
step S3, coating Cu on the copper50Zr43Al7And mixing the metal glass powder and the copper powder to perform discharge plasma sintering to obtain the high-strength high-conductivity metal glass composite material, wherein the sintering temperature is not more than 503 ℃.
According to the technical scheme, the composite powder is prepared by selecting specific metal glass powder and combining a chemical copper plating method, so that the crystalline copper is uniformly and firmly combined with the amorphous metal glass powder better, and the obtained metal glass composite material has high strength and high conductivity. Wherein, the sintering is carried out below the crystallization temperature of the amorphous alloy to avoid crystallization. Compared with other sintering modes, the spark plasma sintering method has the advantages of short sintering time, low sintering temperature and uniform heating inside the sample.
Research workers at home and abroad have conducted a great deal of research in order to develop materials having both high strength and high electrical conductivity in order to obtain materials satisfying the performance requirements of the new generation of electric devices, but research to date has focused on the use of high electrical conductivity materials (copper alloys) as starting materials to expect new high strength and high electrical conductivity materials by means of strengthening, but the requirements have been difficult to satisfy so far for various reasons. In the present invention, we consider in reverse that a metallic glass alloy with ultrahigh strength is used as a starting material, and by improving its conductivity, a novel material satisfying both high strength and high conductivity requirements is expected to be obtained. The success of the technical scheme of the invention can hopefully develop an effective way for preparing the novel composite material with high strength and high conductivity, and has great practical significance for promoting the practical process of using the metal glass as a high-performance structural functional material.
As a further improvement of the present invention, step S1 includes: firstly, preparing Cu by adopting a suspension smelting method50Zr43Al7A mother alloy ingot, and then obtaining Cu by using the prepared mother alloy ingot through an argon atomization method50Zr43Al7Powder particles.
Further, the Cu50Zr43Al7The master alloy ingot is prepared by a suspension smelting method.
Further, in the argon atomization method, the melting temperature of the alloy was about 1280 ℃, and the injection pressure was set to 3.2 MPa.
As a further improvement of the present invention, in step S2, the pre-plating pretreatment includes steps of washing, sensitizing, and activating.
As a further improvement of the invention, the pre-plating pretreatment comprises:
firstly adopting absolute ethyl alcohol to Cu50Zr43Al7Ultrasonic cleaning the powder particles, sensitizing the filtered powder in a mixed solution of stannous chloride and hydrochloric acid, and finally immersing the powder in an aqueous solution containing palladium chloride and hydrochloric acid for activation treatment, wherein the powder is cleaned by deionized water after each step of treatment.
Further, the concentration of the stannous chloride is 5-10g/L, the concentration of hydrochloric acid is 30-50mL/L, and the sensitization time is 5-10 min; in the aqueous solution of palladium chloride and hydrochloric acid, the concentration of the palladium chloride is 0.3-0.5g/L, and the concentration of the hydrochloric acid is 5-10 mL/L.
Preferably, in the mixed solution of stannous chloride and hydrochloric acid, the concentration of the stannous chloride is 10g/L, the concentration of the hydrochloric acid is 40mL/L, and the sensitization time is 10 min; in the aqueous solution of palladium chloride and hydrochloric acid, the concentration of palladium chloride was 0.5g/L and the concentration of hydrochloric acid was 10 mL/L.
As a further improvement of the invention, the reducing agent adopted in the chemical plating process is formaldehyde.
More preferably, the adopted reducing agent is a 37 wt% formaldehyde solution, the concentration of the formaldehyde in the plating solution is 30-50mL/L, and the concentration of the formaldehyde in the plating solution is 0.4-0.7 mol/L.
As a further improvement of the invention, in the chemical plating process, the pH value of the plating solution is 12.0-12.7.
As a further improvement of the invention, in the chemical plating process, the temperature of the plating solution is 50-60 ℃, the pH value of the solution is periodically detected, and when the pH value is too low, 1mol/L NaOH solution is dripped into the solution, and the pH value is kept stable until the reaction is finished.
As a further improvement of the invention, the plating solution is prepared by adopting the following steps:
step S201, adding sodium potassium tartrate into deionized water, stirring until the sodium potassium tartrate is completely dissolved, adding disodium ethylene diamine tetraacetate, stirring until the disodium ethylene diamine tetraacetate is dissolved to form a double-complexing agent solution, and heating the solution to 35-45 ℃; further, the solution was heated to 40 ℃;
step S202, dissolving copper sulfate in ionized water, heating and continuously stirring;
step S203, adding the heated copper sulfate solution into a complexing agent solution to obtain a copper ion complex solution;
step S204, adding potassium ferrocyanide and 2,2' -bipyridine into the copper ion complex solution to form a bi-stabilizer system, and stirring the solution;
step S205, adding the pretreated powder particles into a plating solution, heating to 50-60 ℃, uniformly stirring and mixing, and adding a formaldehyde solution as a reducing agent; and adjusting the pH of the solution.
As a further improvement of the invention, in step S3, Cu is coated with copper50Zr43Al7The metal glass powder and the copper powder are mixed, and the mass percent of the copper powder is 20-50%.
The invention also discloses a high-strength high-conductivity metal glass composite material which is prepared by adopting the preparation method of the high-strength high-conductivity metal glass composite material.
Compared with the prior art, the invention has the beneficial effects that:
by adopting the technical scheme of the invention, the composite powder is prepared by adopting a method of chemically plating copper on specific metal glass powder, so that crystal copper is uniformly and firmly combined with the metal glass powder, and finally mixed with copper powder for sintering to obtain the composite material.
Drawings
FIG. 1 is a diagram of Cu produced by gas atomization in an embodiment of the present invention50Zr43Al7Surface topography SEM image of the powder.
FIG. 2 is a diagram of Cu produced by gas atomization in an embodiment of the present invention50Zr43Al7DSC curve of the powder.
FIG. 3 is a copper clad Cu of an embodiment of the invention50Zr43Al7SEM image of surface morphology of powder, wherein (a) is Cu coated with Cu50Zr43Al7SEM image of the surface morphology of the powder, and (b) is a partially enlarged SEM image of the frame part in (a).
FIG. 4 is a cross-sectional SEM image of an electroless copper powder damascene with epoxy in accordance with an embodiment of the present invention.
FIG. 5 is a copper cladding thickness characterization of electroless copper powder of an embodiment of the invention.
FIG. 6 is a sample of Bulk Metallic Glass Composite (BMGC) and Cu at various copper additions for an example of the present invention50Zr43Al7XRD contrast patterns of Bulk Metallic Glass (BMG) samples.
FIG. 7 is a graph comparing the electrical conductivity of copper-coated metallic glass powder and uncoated metallic glass powder obtained in the examples of the present invention, respectively, with that of copper powder, which was SPS sintered to obtain composite samples.
FIG. 8 shows copper-coated gold obtained in accordance with an embodiment of the present inventionThe composite material sample obtained after the metal glass powder and the uncoated metal glass powder are respectively sintered with copper powder by SPS is 5 multiplied by 10-4s-1Compression curves at constant strain rate are compared.
FIG. 9 is an SEM micrograph of the fracture morphology of sintered samples of copper-clad metallic glass powder and copper powder obtained in accordance with an example of the present invention and the compression fracture surface of a BMGC sample prepared by mixing a comparative example of virgin CuZrAl metallic glass powder and 40 wt.% copper powder, wherein (a) is an SEM micrograph of the compression fracture surface of a BMGC sample prepared by mixing virgin CuZrAl metallic glass powder and 40 wt.% copper powder; (b) the fracture morphology of samples prepared for copper-clad metallic glass powder and copper powder.
FIG. 10 is a comparison graph of the morphology of copper-clad metallic glass frits at different formaldehyde concentrations for examples of the present invention, wherein a) the formaldehyde concentration is 20mL/L, b) the formaldehyde concentration is 30mL/L, and c) the formaldehyde concentration is 40 mL/L.
FIG. 11 is a comparison graph of the topography of copper coated metallic glass powder at different bath pH values for examples of the invention, wherein a) the bath pH is 11.5, b) the bath pH is 12.0, c) the bath pH is 12.7, d) the bath pH is 13.3.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
A high-strength high-conductivity metal glass composite material is prepared by the following steps:
step S1, preparing Cu50Zr43Al7Powder particles;
Cu50Zr43Al7(atomic ratio) preparing a master alloy ingot by using a suspension smelting method according to a nominal proportion, and preparing the prepared alloy into spherical particle powder by using an argon atomization method, wherein the melting temperature of the alloy is about 1280 ℃, and the injection air pressure is set to be 3.2 MPa.
Step S2, Cu obtained in step S150Zr43Al7Pretreating the powder particles before plating, then carrying out chemical plating, cleaning and drying to obtain the Cu coated with copper50Zr43Al7Metallic glass powder.
In order to ensure that the crystal copper is uniformly and firmly combined with the metal glass powder, the composite powder is prepared by adopting a metal glass powder chemical copper plating method. Before starting electroless copper plating, the original powder needs to be pretreated before plating, and the pretreatment can be divided into three steps of cleaning, sensitizing and activating. The powder was ultrasonically cleaned with absolute ethanol for half an hour at room temperature, and the filtered powder was placed in 10g/L stannous chloride (SnCl)2) And 40mL/L hydrochloric acid for 10min, and finally immersing the amorphous powder in a solution containing 0.5g/L palladium chloride (PdCl)2) And 10mL/L hydrochloric acid in water solution for activation treatment. After each step of treatment, the powder is washed by deionized water to eliminate the influence of impurity ions. After the pretreatment, the amorphous powder is introduced into an electroless plating solution for electroless copper plating.
The electroless plating solution was formulated as follows.
(1) Firstly, adding weighed potassium sodium tartrate into a certain amount of deionized water, stirring until the potassium sodium tartrate is completely dissolved, then adding ethylene diamine tetraacetic acid, stirring until the ethylene diamine tetraacetic acid is dissolved, forming a double-complexing agent solution, placing the solution in a constant-temperature water bath furnace, and heating the solution to 40 ℃;
(2) dissolving weighed copper sulfate with deionized water, and heating in a constant-temperature water bath at 40 ℃;
(3) adding the heated copper sulfate solution into the complexing agent solution, slowly adding the copper sulfate solution, and slowly stirring the mixture while adding the copper sulfate solution to ensure that copper ions fully form a copper ion complex;
(4) adding weighed potassium ferrocyanide and 2,2' -bipyridine into the solution to form a bistable agent system, and then slowly stirring the solution for 5 min;
(5) adding the powder particles subjected to the pre-plating treatment into a plating solution, heating to 50-60 ℃, fully stirring and mixing, and adding a formaldehyde solution serving as a reducing agent with the concentration of 40 ml/L;
(6) adding weighed sodium hydroxide into the solution, and adjusting the pH value to 12.0-12.7;
in the chemical plating process, the temperature of the solution is ensured to be 50-60 ℃; and simultaneously, measuring the pH value of the solution once every 3min by using a pH tester, and when the pH value is too low, dropwise adding 1mol/L NaOH solution into the solution to keep the pH value stable until the reaction is finished. And (3) continuously stirring by using a magnetic stirrer in the whole copper plating process, and finishing the chemical copper plating after the solution does not bubble for 5min any more. And filtering the plated powder, washing the powder by using deionized water, and finally drying the powder in vacuum to obtain the copper-coated metal glass powder.
Step S3, coating Cu on the copper50Zr43Al7And mixing the metal glass powder and the copper powder to perform discharge plasma sintering to obtain the high-strength high-conductivity metal glass composite material.
The composite powder copper powder prepared by chemical plating is mixed and is subjected to Spark Plasma Sintering (SPS), and compared with other sintering modes, the SPS has the advantages of short sintering time, low sintering temperature and uniform heating inside a sample. Firstly, putting the weighed powder into a tungsten carbide mould, loading a certain pressure and pre-compacting. Then sintering the mixture by using SPS under the loading pressure of 300 MPa. To avoid crystallization, the sintering is carried out at the crystallization temperature (T) of the amorphous alloyX) In the present example, the temperature was set at 420 ℃ and the temperature was maintained for 10 min. And cooling the furnace to room temperature to obtain a sintered sample. The sample was shaped as a cylinder 15mm in diameter and about 5mm thick and had a mass of about 6 g.
In this example, different copper contents were selected and mixed with the obtained copper-clad metallic glass powder for sintering, wherein the copper contents were 20 wt.%, 30 wt.%, 40 wt.%, and 50 wt.%, respectively, and the obtained composite materials with different copper contents were analyzed for influences on electrical conductivity and mechanical properties, as shown in table 1.
TABLE 1 comparison of composite Properties for different copper contents
As can be seen from the comparison of the properties in table 1, by adding copper in different contents, a metallic glass composite material having both conductivity and high strength and high plasticity is prepared. During the preparation process, the metal glass crystallization phenomenon does not occur, and the plasticity and the conductivity of the composite material are continuously increased along with the increase of the copper content. The final test result shows that the copper accounts for 30-50% by mass, has better conductivity and good Young modulus and compressive plastic strain performance. At a copper content of 50 wt.%, the metal glass composite has the best overall properties.
In step S1, Cu prepared by gas atomization50Zr43Al7Surface morphology of the powder copper-coated metallic glass powder was subjected to surface morphology analysis and DSC analysis, and the results are shown in FIGS. 1 and 2, and the glass transition temperature (T) of the powder was obtained from the results of the differential scanning calorimetry analysis of FIG. 2g) At 442 ℃ and a crystallization temperature (T)X) The temperature was 503 ℃. In step S3, the temperature of the plasma sintering is determined according to the crystallization temperature of the powder obtained in step S1, and may be lower than the crystallization temperature of the powder.
In step S2, Cu coated with copper50Zr43Al7The surface morphology of the powder is analyzed by an electron microscope, and the result is shown in fig. 3, so that the copper plating layer is uniformly and densely distributed on the surface of the amorphous matrix, and no plating leakage phenomenon is found. It can be observed from the enlarged view that the copper particles generated by the electroless plating are about several hundred nanometers to one micrometer, and the copper particles are gradually generated along with the reaction in the electroless plating process and are adhered to the surface of the amorphous powder layer by layer at the positions with the catalytic active sites, so that the surface of the powder has the granular texture.
In addition, Cu coated with copper inlaid with epoxy resin50Zr43Al7The powder, after brittle fracture, was analyzed by electron microscopy for cross-section and the thickness of the copper cladding was characterized, as shown in fig. 4 and 5, it can be seen that Cu50Zr43Al7The surface of the powder is uniformly coated with a compact copper-plated layer, and the thickness of the copper-coated layer is characterized to be about 1 micron.
In step S3, Bulk Metallic Glass Composite (BMGC) samples and Cu were prepared for different copper additions50Zr43Al7A comparative XRD analysis of Bulk Metallic Glass (BMG) samples was performed, as shown in fig. 6, and it can be seen that the sintered CuZrAl bulk amorphous (CuZrAl BMG, Cu ═ 0) showed a typical amorphous state, and no other peaks (sharp diffraction peaks corresponding to crystalline copper phases) were found except for broad diffuse scattering peaks, indicating that no crystalline phase precipitation occurred during SPS sintering. In the copper-containing composite material, the diffraction peak of the copper crystal was stronger as the copper content was increased, and no Cu was found2And other crystal phases such as O and the like exist, which indicates that no oxidation reaction is carried out during the sintering process to separate out the phases.
Copper-coated Cu obtained for the present example50Zr43Al7The conductivity of the composite material samples obtained by sintering the metal glass powder and copper with different contents by SPS is detected, and uncoated Cu is used at the same time50Zr43Al7Composite samples obtained by SPS sintering metallic glass powder with different amounts of copper were used as comparative examples, and the results are detailed in FIG. 7 (reference is made to standard annealed pure copper, which is generally defined as 100% IACS in conductivity, i.e. 5.80E +7(1/Ω. m), at 5X 10-4s-1A plot of the compression curve at a constant strain rate is shown in fig. 8. From FIG. 7, it can be seen that Cu is coated with copper50Zr43Al7The metallic glass powder has better electrical conductivity and the electrical conductivity increases with the increase of the added copper content, while, as can be seen in fig. 8, the sintered CuZrAl bulk amorphous exhibits a strength of about 1600MPa and no plastic deformation before compressive fracture occurs. When the amount of Cu added is less than 30 wt.%, the compression process of the bulk amorphous composite does not show significant plastic deformation, and the samples of the bulk amorphous composite prepared with the Cu-coated amorphous powder show similar compressive fracture strength to the uncoated powder. A sample of bulk amorphous composite material not plated with copper with a copper mass fraction of 40% showed a breaking strength of about 700MPa and a plastic strain of about 5.8%. And the block amorphous composite material sample prepared from the electroless copper plating amorphous powder with the same mass fraction has higher compression plasticity of 7.4 percent and does not influence the strength.
In addition, comparing the compression fracture surface morphology of BMGC samples prepared by mixing the virgin CuZrAl metallic glass powder and 40 wt.% copper powder with the fracture morphology of samples prepared from copper-clad metallic glass powder and copper powder, as shown in fig. 9(a), a weaker interfacial bond is clearly shown between the amorphous and copper that are not chemically plated, so that cracks propagate along the interface, resulting in a cracking phenomenon at the interface, and the smooth surface of the amorphous is exposed, which is a major cause of the reduction of the compression fracture strength. Fig. 9(b) is a graph showing that after the original amorphous powder was treated by electroless copper plating, almost no exposed surface was found due to the close bonding of the interface on the fracture surface of the bulk amorphous composite specimen with copper, which is the reason for higher conductivity and higher plasticity. In addition, the large area creep deformation observed also indicates ductile fracture.
The comparison of the electrical property and the mechanical property of the amorphous alloy composite material with copper content of 40-50% obtained in this example with other conventional composite materials is shown in table 2.
TABLE 2 comparison of electrical and mechanical properties of amorphous alloy composites with beryllium bronze and copper-based composites
As can be seen from table 2, the amorphous alloy composite material of the present embodiment has higher strength, hardness and compactness under the condition of higher electrical conductivity. The currently used copper-beryllium alloy in table 2 has beryllium element which is harmful to human body, and the combination property is not the best, and needs to be improved by subsequent aging treatment. The ceramic particle reinforced composite material in the research has two biggest problems, namely, the sintering density is difficult to improve due to the irregular shape of the ceramic particle reinforced composite material, and the strength is difficult to improve. The carbon nanotube or graphene reinforced composite material has a wider difference to the use requirement. The invention uses the amorphous alloy with specific components prepared by the invention, so that the composite material is completely compact and the strength is greatly improved on the basis of ensuring better conductivity, and the composite material can have more excellent comprehensive performance if the composite material is subjected to processes such as rolling deformation and the like at a later stage.
Furthermore, the influence of the concentration of formaldehyde as a reducing agent and the pH value of the plating solution on the stability of the plating solution in the chemical plating process is researched, and the concentrations of the reducing agent are selected from 20mL/L, 30mL/L and 40 mL/L; the pH values of the plating solutions were selected from 11.5, 12.0, 12.7 and 13.3. And the plating effect of the powders under different conditions was compared.
FIG. 10 shows the powder surface morphology of electroless copper plated after addition of different concentrations of formaldehyde. It can be seen from fig. 10 that the copper plating layer is more and more well combined with the amorphous powder and the copper layer is more dense as the concentration of formaldehyde is increased. When the concentration of formaldehyde is 20mL/L, part of the plating layer presents a phenomenon of 'shelling', and part of the powder surface is not completely plated; with the increase of the concentration of the formaldehyde to 30mL/L, no obvious shelling phenomenon is found, but partial powder surface is still found to be not completely coated, and the partial coating is rougher; when the concentration is 40mL/L, the coating layer on the surface of the powder is obviously dense and smoother, and the phenomenon that the surface of the powder is not coated rarely occurs. In general, when the formaldehyde concentration is more than 20mL/L, the effect of electroless copper plating is obviously improved along with the increase of the formaldehyde concentration. The reason is that the higher formaldehyde concentration accelerates the reaction rate, accelerates the copper deposition speed, the reacted copper microparticles are covered by the copper generated by the subsequent reaction without being oxidized, and the higher the formaldehyde content is, the more thorough the reaction is carried out, the higher the copper content is, so that the more dense and bright copper layer is coated on the surface of the amorphous powder when the concentration is 40 mL/L.
Since the experiment uses an alkaline plating solution, the pH value is an important factor in the electroless copper plating process, and the redox reaction can only be started after the pH value is more than 11. If the pH value is too low, the reaction speed is too slow, so that the deposition speed of the copper plating layer is slow, copper can be deposited on the inner wall or the bottom of the reaction container, and the sample can be polluted because the copper simple substance on the inner wall of the container peels off and enters the plating solution while the deposition amount of the copper on the particle surface is reduced. However, if the pH is too high, the reaction is too severe, resulting in deposition of copper near the particle surface and deposition of a large amount of copper in the plating solution, which results in poor plating effect.
As shown in fig. 11, SEM photographs of composite powders obtained by performing the reaction at four different phs are shown. At a pH of 11.5, due to OH contained in the solution－The concentration is low, so that the total reaction is not completely carried out, and only a small amount of copper is generated, so that the surface of a large amount of powder is not coated with copper; at a pH of 13.3, it was found that a large amount of free copper flakes were produced and could not be coated on the amorphous powder matrix, probably because the reaction rate was too fast to stabilize and the produced copper flakes were loose and coarse. In contrast, when the pH value is 12.0 or 12.7, the copper cladding layer generated by the reaction is more compact and has better cladding effect.
Corresponding experiments were performed on the copper plating content of the obtained copper-coated metallic glass powder for different pH values of the plating solution and different reaction times, and the results are shown in table 3.
TABLE 3 copper plating content of copper-coated metallic glass powders at different pH
As can be seen from Table 3, the higher the pH, the shorter the reaction time, and the degree of shortening was significant. With the increase of pH, the copper plating content of the composite powder after chemical plating is higher and higher. Referring to fig. 11, in which fig. 11d) shows that most of the copper particles and clusters are not coated, although the copper content is high.
In the prior art, high-strength and high-conductivity composite materials are all made of high-conductivity materials, and better comprehensive performance is obtained by various strengthening means. In the invention, from the aspect of starting materials, the novel composite material with both high strength and high conductivity is obtained by using high-strength metal glass as the starting material and improving the conductivity of the metal glass. The chemical plating method improves the interface combination of the metal glass and the copper, reduces the interface resistance, improves the conductivity and simultaneously achieves the aim of improving the strength. By adopting the spark plasma sintering SPS method, low-temperature rapid sintering can be realized, amorphous crystallization is avoided, and high strength of the reinforced phase particles is ensured, so that in the composite material with the copper content of 40 wt.%, the electric conductivity can reach 22.06% IACS, and the compressive strength is close to 700 MPa.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of a metal glass composite material with high strength and high conductivity is characterized by comprising the following steps: the method comprises the following steps:
step S1, preparing Cu50Zr43Al7Powder particles;
step S2, for the Cu obtained in step S150Zr43Al7Pretreating the powder particles before plating, then carrying out chemical plating, cleaning and drying to obtain the Cu coated with copper50Zr43Al7A metallic glass powder;
step S3, coating Cu on the copper50Zr43Al7And mixing the metal glass powder and the copper powder to perform discharge plasma sintering to obtain the high-strength high-conductivity metal glass composite material, wherein the sintering temperature is not more than 503 ℃.
2. The method for preparing a high-strength high-conductivity metal glass composite material according to claim 1, wherein the step S1 includes: firstly, preparing Cu by adopting a suspension smelting method50Zr43Al7A mother alloy ingot, and then obtaining Cu by using the prepared mother alloy ingot through an argon atomization method50Zr43Al7Powder particles.
3. The method for preparing a high-strength high-conductivity metal glass composite material according to claim 1, wherein in step S2, the pre-plating pretreatment comprises the steps of cleaning, sensitizing and activating.
4. The method of claim 3, wherein the pre-plating pretreatment comprises:
firstly adopting absolute ethyl alcohol to Cu50Zr43Al7Ultrasonically cleaning powder particles, sensitizing the filtered powder in a mixed solution of stannous chloride and hydrochloric acid, and finally soaking the powder into an aqueous solution containing palladium chloride and hydrochloric acid for activation treatment, wherein the powder is cleaned by deionized water after each step of treatment; in the mixed solution of stannous chloride and hydrochloric acid, the concentration of the stannous chloride is 5-10g/L, the concentration of the hydrochloric acid is 30-50mL/L, and the sensitization time is 5-10 min; in the aqueous solution of palladium chloride and hydrochloric acid, the concentration of the palladium chloride is 0.3-0.5g/L, and the concentration of the hydrochloric acid is 5-10 mL/L.
5. The method of preparing a high strength high conductivity metallic glass composite as claimed in claim 1, wherein: in the chemical plating process, the adopted reducing agent is formaldehyde, and the concentration of the formaldehyde in the plating solution is 0.4-0.7 mol/L.
6. The method for preparing a high-strength high-conductivity metal glass composite material according to claim 5, wherein the pH value of the plating solution is 12.0 ~ 12.7.7 during the electroless plating process.
7. The method of preparing a high strength high conductivity metallic glass composite as claimed in claim 6, wherein: in the chemical plating process, the temperature of the plating solution is 50-60 ℃, the pH value of the solution is periodically detected, when the pH value is too low, 1mol/L NaOH solution is dripped into the solution, and the pH value is kept stable until the reaction is finished.
8. The method of preparing a high strength high conductivity metallic glass composite as claimed in claim 7, wherein: the plating solution is prepared by the following steps:
step S201, adding sodium potassium tartrate into deionized water, stirring until the sodium potassium tartrate is completely dissolved, adding disodium ethylene diamine tetraacetate, stirring until the disodium ethylene diamine tetraacetate is dissolved to form a double-complexing agent solution, and heating the solution to 35-45 ℃;
step S202, dissolving copper sulfate in deionized water and stirring;
step S203, adding the heated copper sulfate solution into a complexing agent solution to obtain a copper ion complex solution;
step S204, adding potassium ferrocyanide and 2,2' -bipyridine into the copper ion complex solution to form a bi-stabilizer system, and stirring the solution;
step S205, adding the pretreated powder particles into a plating solution, heating to 50-60 ℃, uniformly stirring and mixing, and adding a formaldehyde solution as a reducing agent; and adjusting the pH of the solution.
9. The method of claim 1 ~ 7, wherein in step S3, the Cu is coated with copper50Zr43Al7The metal glass powder and the copper powder are mixed, and the mass percent of the copper powder is 20 ~ 50%.
10. The high-strength high-conductivity metal glass composite material is characterized by being prepared by the preparation method of the high-strength high-conductivity metal glass composite material as claimed in any one of claims 1 ~ 9.
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| CN112974798A (en) * | 2021-02-05 | 2021-06-18 | 哈尔滨工业大学 | Method for dustless treatment of beryllium powder |
| CN113388750A (en) * | 2021-06-22 | 2021-09-14 | 哈尔滨工业大学（深圳） | Metal glass particle reinforced nanocrystalline copper alloy composite material and preparation method thereof |
| CN114277278A (en) * | 2021-12-29 | 2022-04-05 | 九江天时粉末制品有限公司 | Wear-resistant aluminum bronze plate and preparation method thereof |
| CN115058615A (en) * | 2022-07-01 | 2022-09-16 | 哈尔滨工业大学（深圳） | Preparation method of copper-based metal glass composite material with multi-scale structure |
| CN115058615B (en) * | 2022-07-01 | 2023-11-10 | 哈尔滨工业大学（深圳） | Preparation method of copper-based metallic glass composite material with multi-scale structure |
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