CN114086023A - Method for preparing copper-based electric contact material based on foaming infiltration process and product thereof - Google Patents
Method for preparing copper-based electric contact material based on foaming infiltration process and product thereof Download PDFInfo
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- CN114086023A CN114086023A CN202111328282.4A CN202111328282A CN114086023A CN 114086023 A CN114086023 A CN 114086023A CN 202111328282 A CN202111328282 A CN 202111328282A CN 114086023 A CN114086023 A CN 114086023A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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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
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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
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
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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
- B22F3/10—Sintering only
- B22F3/1035—Liquid phase sintering
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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
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
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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
- B22F3/24—After-treatment of workpieces or articles
- B22F3/26—Impregnating
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/025—Composite material having copper as the basic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
Abstract
The invention discloses a preparation method of a framework for a copper-based electric contact material infiltration preparation process, which comprises the steps of adding a foaming agent into Cu-based mixed powder for sintering reinforcement, wrapping a sintering-reinforced Cu-based powder with a separant, sintering the Cu-based powder to a liquid phase, crushing and screening to obtain a high-strength porous Cu-based powder, pressing the porous Cu-based powder into the framework, spraying silicon-containing corundum powder on a framework working surface, arranging a pure copper sheet above the framework, and carrying out liquid-phase infiltration on the framework at a high temperature to obtain the Cu-based electric contact material with high copper content and low resistivity. The invention solves the problem that the high-copper-content Cu-based electric contact material can only be manufactured by adopting a solid-phase sintering process, and compared with the Cu-based electric contact material with the same copper content prepared by adopting the sintering process, the high-copper-content Cu-based electric contact material has higher density and burning loss resistance, lower resistivity and surface oxidation resistance, and greatly improved service performances such as electric service life and the like.
Description
Technical Field
The invention relates to the field of electrical contact materials, in particular to a method for preparing a copper-based electric contact material based on a foaming infiltration process and a product thereof.
Background
Copper-based contact materials are widely applied as contacts in low-voltage circuit breakers, frame circuit breakers, direct-current relays and the like, are generally manufactured by an infiltration method, and have the content of refractory phases (W, WC and Mo) between 40 and 80 weight percent. On the other hand, in the situation with high temperature rise requirement, for example, the contact resistance of the material with the refractory phase content higher than 40 wt% in the direct current relay is difficult to meet the use requirement, and the contact with the high copper content can only adopt the solid phase sintering mode to have insufficient burning loss resistance, and can not meet the requirements of short circuit resistance and electric service life performance of the switch, thereby seriously restricting the development of the industry.
The powder metallurgy process is adopted to prepare the electric contact material, and the infiltration process is well known to obtain the optimal material performance. Compared with a solid-phase sintering process, the density, the hardness, the conductivity and the bonding strength of the material prepared by the infiltration process are obviously improved, and the porosity is obviously reduced; the electric arc burning resistance and the mechanical abrasion resistance of the corresponding contact material are obviously improved. However, the preparation of the electric contact material by the infiltration process can be realized only when the material meets certain characteristics, and can only be prepared by adopting a solid-phase sintering mode under the unsatisfiable condition. The electric contact material needs to meet the following characteristics and is prepared by adopting an infiltration process:
1. in order to ensure the shape of a semi-finished product after infiltration, the volume of infusible particles in the framework is more than 25 percent in the infiltration process;
2. the framework has better wettability with the infiltration metal;
3. the skeleton and the infiltration metal are not mutually fused or have small solubility.
The copper-based contact material having a low copper content, such as CuW50, CuW55, CuW60, CuWC50, CuWC60, CuMo40, CuMo50, and CuMo60, generally adopts an infiltration process, and the copper-based contact material having a high copper content, such as CuW15, CuW25, CuW30, CuW35, CuWC15, CuW30, CuMo20, and CuMo30, cannot satisfy the infiltration condition (1), and is manufactured by a solid-phase sintering-co-pressing process or a solid-phase sintering-extrusion process.
The invention discloses a Chinese patent with publication number CN108441668A, and provides an AgWNiC material, which relates to a gas pressure infiltration process, because the problem that the volume of infusible particles in a framework is more than 25% in the infiltration process is not solved, a solid phase sintering process with the temperature of 800-900 ℃ is selected when the tungsten content is 12-25 wt%, and a gas pressure infiltration process is selected when the tungsten content is more than 25 wt% and contains graphene, nickel and the like. Although graphite alkene can increase the infusible phase volume, also can increase resistance simultaneously, owing to with graphite alkene and the nonwetting characteristic of silver liquid under the ordinary pressure, can cause silver liquid phase to ooze out from the skeleton backward behind the sintering liquid phase temperature simultaneously, seriously influence material bonding strength and resistivity, the intervention of external pressure has certain improvement to bonding strength harmfully, nevertheless can't avoid completely. The process conditions of the infiltration temperature of 980-1100 ℃ and the gas pressure of 100MPa-1GPa can be realized only by a hot isostatic pressing machine, and the process cost is too high. Graphite will react with tungsten at 1100 ℃, and the actual final material is silver tungsten carbide rather than silver tungsten graphite.
The Chinese patent with publication number CN110373566A provides a manufacturing process of AgWC (W), which relates to a method for manufacturing an electrical contact material by infiltrating and densifying AgWC (W) material, crushing the AgWC (W) material, and mixing the AgWC (W) material with C, Ag according to a certain proportion. The mode is that the manufactured product contains partial infiltration tissues, the main structure is still a solid-phase sintering tissue, and the tissue uniformity is difficult to ensure. Meanwhile, due to the high ductility and toughness of silver and the high strength of WC (W), the crushing process of the AgWC (W) infiltration compact material is very difficult, the crushing into powder with ideal granularity is more difficult, and the process is difficult to realize large-scale production.
According to the Chinese patent publication No. CN104209520A, pores are increased by adding a polyacrylate pore-forming agent into powder, the strength of the powder prepared by the method is low, the production requirement can be met when Cu (W, WC and Mo)40 and a copper-based material with lower Cu content are prepared, and when the Cu-based material with the copper content higher than 40 percent is prepared, the framework collapse and even burst and cannot be formed due to severe deformation of the pores in the infiltration process.
The invention patent of China with publication number CN112548099A provides a method for preparing porous alloy powder by adopting an ammonium bicarbonate foaming agent, the powder prepared by the method also has the problem of low internal strength of the powder, and in the process of infiltrating Cu (W, WC and Mo) with high copper content, the powder can cause framework collapse or even explosion due to severe deformation of pores and cannot be formed, and the mechanism of the method is basically similar to that of a polyacrylate pore-forming agent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a copper-based electric contact material based on a foaming infiltration process and a product thereof. The foaming infiltration process is a breakthrough innovation of the traditional infiltration process, provides a new idea and method for preparing the copper-based electric contact material with low resistivity and high copper content, and has higher density and burning loss resistance, lower resistivity and surface oxidation resistance, greatly improved service performances such as electric service life and the like compared with the Cu-based electric contact material with the same copper content prepared by the traditional sintering process.
In order to achieve the purpose, the technical scheme of the invention comprises the following steps:
(1) foaming: adding a foaming agent into the copper-based mixed powder, uniformly stirring and sieving to obtain copper-based mixed powder particles wetted by the foaming agent, and heating and foaming the sieved copper-based mixed powder particles in an oven;
(2) solid-phase sintering and strengthening: solid-phase sintering the copper-based mixed powder particles foamed in the step (1) to form fixed pores inside the particles;
(3) packaging release agent: heating and stirring the copper-based mixed powder particles sintered and reinforced in the step (2) in a stirrer, and spraying a paraffin solution at the same time to wrap the powder by the paraffin and dry a solvent of the paraffin solution in the stirring process;
(4) powder liquid phase sintering: carrying out high-temperature liquid phase sintering on the copper-based mixed powder particles coated with paraffin in the step (3), and crushing and screening the sintered powder to obtain high-strength porous prefabricated powder with good fluidity;
(5) pressing: and pressing and molding the porous prefabricated powder into a framework.
Further setting the adding amount of the foaming agent in the step (1) to be 1: 100-1000, wherein the spraying amount of the paraffin solution in the step (3) is 1:100-1:500 according to the mass ratio of the paraffin to the powder.
The copper-based mixed powder is further provided, the Cu content is 50 wt% -70 wt%, and the balance is one or a combination of W, WC and Mo.
The foaming agent is one or a combination of ammonium bicarbonate, ammonium carbonate, ammonium hydrogen oxalate and ammonium oxalate.
Further setting that the powder screening process in the step (1) is 100-mesh and 300-mesh screening, and the post-screening foaming process is as follows: the foaming temperature is 60-200 ℃, and the foaming time is 30-60 minutes.
The solid phase sintering process in the step (2) is further set as follows: the sintering temperature is 500-800 ℃, the sintering time is 30-120 minutes, and the sintering atmosphere is reducing or vacuum atmosphere.
The further setting is that the heating temperature in the step (3) is 60-100 ℃, the paraffin content in the paraffin-containing solution is 1-10 wt%, and the solvent is gasoline.
The liquid phase sintering process in the step (4) is further set as follows: the gradient sintering process includes sintering at 400-500 deg.c for 60-120 min, sintering at 600-700 deg.c for 60-120 min, sintering at 800-900 deg.c for 60-120 min, and sintering at 1100-1300 deg.c for 60-120 min in reducing atmosphere or vacuum atmosphere.
The liquid phase sintering and screening process in the step (4) is further set to be a 50-100 mesh screen
In addition, the invention also provides a method for preparing the copper-based electric contact material based on the foaming infiltration process, which is characterized in that based on the skeleton prepared by the method, the pure copper sheet is added on the skeleton, silicon-containing corundum powder is sprayed on the skeleton, and the copper-based electric contact material is obtained by infiltration in an infiltration furnace.
Further setting the infiltration temperature to be 1100-1300 ℃, the infiltration time to be 60-120 minutes, and the infiltration atmosphere to be vacuum atmosphere;
the further setting is that the granularity of the corundum powder for spraying is 200-500 meshes, the alumina content of the corundum powder for spraying is more than or equal to 85wt percent, and the balance is Si.
The electric contact material after infiltration is further provided with one of CuW (30-35), CuWC (20-25) and CuMo (25-30) according to the mass ratio.
In addition, the invention also provides the copper-based electric contact material prepared by the method.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a Cu-based electric contact material by an infiltration process, which is used for preparing the Cu-based electric contact material by the infiltration process with high copper content and low resistance, wherein the copper content of the material is 70-75 wt%, the high copper content ensures low and stable contact resistance in the electric contact process and lower bulk resistance, the temperature rise of a contact in the electric contact process can be ensured to be low and stable, the electric arc burning loss resistance and the mechanical wear resistance of the material are ensured by adopting an infiltration mode, and the electric service life of the material is prolonged.
2. The high-strength porous powder is prepared and used as a matrix material of a product framework, and more liquid copper is filled in the pores of the high-strength framework in the infiltration process, so that the requirement of the infiltration process on the volume of a solid phase is met. The high-temperature stability of the porous powder is ensured by adopting the liquid phase sintering process, and the powder does not have the adverse phenomena of severe particle rearrangement, deformation, collapse and the like in the liquid phase sintering process, so that the stability of the matrix skeleton shape in the infiltration process is ensured, and the infiltration process can be smoothly carried out. The high framework porosity can cut the distribution of liquid copper in the electric contact process, and prevent the fusion welding phenomenon caused by the aggregation of local liquid copper in the effective contact area of the moving contact and the static contact.
3. In order to realize the preparation of the high-strength porous powder particles, the foaming material is used as an expanding agent for sintering the Cu-based powder particles, so that the size of the internal pores of the Cu-based powder is increased, and the filling of more copper liquid in the infiltration process is facilitated. Paraffin wrapped outside the powder particles is used as an isolating agent, so that the problem that the particles cannot be broken and separated due to the fact that liquid-phase copper bridges are formed among the particles in the liquid-phase sintering process of the powder particles is solved. The paraffin is selected as the wrapping isolating agent because the paraffin is strong in wrapping performance by spraying, the wrapped powder is mutually isolated, the paraffin is slowly decomposed in the gradient sintering process before liquid phase sintering, the residue of the trace graphite film remained after decomposition has good anti-bonding capability, the problem that copper bridge adhesion is difficult to break and separate in the liquid phase sintering process of powder particles can be solved, and meanwhile, the trace graphite residue is broken and granulated and separated and broken by pressing a framework film, so that the infiltration process is not influenced.
4. The silicon-containing corundum powder is sprayed on the surface of the copper-based framework material before infiltration, the corundum powder, Cu and refractory phases of the Cu are not reacted, and the corundum powder is not bonded under the condition of complete non-wetting high temperature, so that excessive Cu can be effectively prevented from being enriched to a working surface to cause product failure, and meanwhile, silicon in the powder and Cu on the surface layer of a contact form CuSi alloy through diffusion during infiltration, and the high-temperature oxidation resistance of the surface of the material is improved.
5. The particle size distribution of the sintered powder can be adjusted by adjusting the amount of the foaming agent and the release agent and the liquid phase sintering temperature, and the addition amount of the foaming agent and the release agent and the liquid phase sintering temperature in the method are the optimal choices comprehensively considered in multiple aspects such as bulk particle flowability, powder friability, framework weight stability, framework infiltration stability and the like through multiple experiments.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is an SEM topography 500X of a liquid phase sintered porous powder provided by an embodiment of the invention;
FIG. 2 is an SEM topography 2000X of a liquid phase sintered porous powder provided by an embodiment of the invention;
fig. 3 is a gold phase diagram 500X after infiltration of the contact material according to the embodiment of the present invention, in which a structure after infiltration of coarse porous powder is shown in a dotted line, and a light-colored substance is a silver liquid filled in pores in the structure. The tissue outside the dotted line is fine particle porous powder tissue which is distributed around the coarse particles and plays a role in filling the skeleton.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example one
Weighing 5kg of CuW50 mixed powder, respectively adding 50g of 5 wt% ammonium bicarbonate solution and 5 wt% ammonium carbonate solution, uniformly stirring, and sieving the stirred powder by using a 300-mesh stainless steel sieve to obtain CuW powder particles coated by a foaming agent;
putting the screened powder into a graphite boat, transferring the graphite boat into a vacuum oven, heating the graphite boat to 200 ℃, preserving heat for 60 minutes, transferring the foamed powder and the graphite boat into a hydrogen atmosphere sintering furnace, sintering the graphite boat at 800 ℃, and preserving heat for 30 minutes;
stirring the sintering-strengthened powder in a stirrer, heating the powder, spraying 0.5kg of 10 wt% paraffin-gasoline solution, completely wrapping the powder, and heating and stirring until the gasoline in the powder is dried;
loading the calcined paraffin coated powder into a boat, sintering at 400 ℃, 120 minutes, 600 ℃, 120 minutes, 800 ℃, 120 minutes, 1300 ℃, 60 minutes in a hydrogen atmosphere, cooling, crushing and sieving with a 100-mesh sieve after sintering to obtain high-strength porous prefabricated CuW50 powder with fluidity;
pressing porous prefabricated CuW50 powder into a CuW50 porous framework with the single weight of 10g, spraying 200-mesh alumina powder containing 15 wt% of silicon on the surface of the framework until the surface is completely covered, arranging a pure copper sheet with the single weight of 4.28g on the CuW50 porous framework, and carrying out infiltration in a vacuum infiltration furnace at the infiltration temperature of 1300 ℃ for 120 minutes to obtain an infiltration method CuW35 contact material;
the contact material of the infiltration method CuW35 is tested to have the resistivity of 2.21 mu omega cm reduced by 0.29 mu omega cm compared with the resistance of 2.50 mu omega cm compared with the sintering method.
Example two
Weighing 5kg of CuW40 mixed powder, respectively adding 100g of 2 wt% ammonium oxalate solution, 2 wt% ammonium hydrogen oxalate solution, 2 wt% ammonium bicarbonate solution and 2 wt% ammonium carbonate solution, uniformly stirring, and sieving the stirred powder by using a 200-mesh stainless steel sieve to obtain CuW powder particles coated by a foaming agent;
putting the screened powder into a graphite boat, transferring the graphite boat into a vacuum oven, heating the graphite boat to 150 ℃, preserving heat for 50 minutes, transferring the foamed powder and the graphite boat into an ammonia decomposition furnace, sintering the powder and the graphite boat for 700 ℃, and preserving heat for 50 minutes;
stirring the sintering-strengthened powder in a stirrer, heating the powder, spraying 0.6kg of 3% paraffin-gasoline solution, completely wrapping the powder, and heating and stirring until the gasoline in the powder is dried;
loading the calcined paraffin coated powder into a boat, sintering in a hydrogen atmosphere, cooling, crushing and sieving by a 60-mesh sieve after sintering, wherein the sintering process is 450 ℃, 60 minutes, 650 ℃, 60 minutes, 850 ℃, 60 minutes and 1250 ℃, and the high-strength porous prefabricated CuW40 powder with fluidity is obtained;
pressing porous prefabricated CuW40 powder into a CuW40 porous framework with the single weight of 6g, spraying 400-mesh alumina powder containing 10 wt% of silicon on the surface of the framework until the surface is completely covered, arranging a pure copper sheet with the single weight of 2g on the CuW40 porous framework, and carrying out infiltration in a vacuum infiltration furnace at the infiltration temperature of 1150 ℃ for 80 minutes to obtain an infiltration method CuW30 contact material;
the resistivity of the contact material tested by the infiltration method CuW30 is reduced by 0.27 mu omega cm compared with the resistivity of 2.31 mu omega cm compared with the sintering method.
EXAMPLE III
Weighing 10kg of CuMo32 mixed powder, respectively adding 200g of 2 wt% ammonium oxalate solution, 2 wt% ammonium hydrogen oxalate solution, 4 wt% ammonium bicarbonate solution and 4 wt% ammonium carbonate solution, uniformly stirring, and sieving the stirred powder by using a 120-mesh stainless steel sieve to obtain CuMo powder particles wrapped by a foaming agent;
putting the screened powder into a stainless steel boat, transferring the stainless steel boat into a vacuum oven, heating the stainless steel boat to 120 ℃, preserving heat for 40 minutes, transferring the foamed powder and the stainless steel boat into a vacuum sintering furnace, sintering the powder and the stainless steel boat in the vacuum sintering furnace for 750 ℃, and preserving heat for 45 minutes;
stirring the sintering-strengthened powder in a stirrer, heating the powder, spraying 0.5kg of 8% paraffin-gasoline solution, completely wrapping the powder, and heating and stirring until the gasoline in the powder is dried;
sintering the powder packed corundum boat subjected to the calcined paraffin coating treatment in a hydrogen atmosphere, wherein the sintering process comprises the steps of 500 ℃, 120 minutes, 700 ℃, 120 minutes, 900 ℃, 120 minutes and 1200 ℃, and 120 minutes, and after sintering, cooling, crushing and sieving by a 80-mesh sieve to obtain high-strength porous prefabricated CuMo32 powder with fluidity;
pressing porous prefabricated CuMo32 powder into a CuMo32 porous framework with the single weight of 8g, spraying 500-mesh silicon-containing 8 wt% alumina powder on the surface of the framework until the surface is completely covered, arranging a pure copper sheet with the single weight of 2.24g on the CuMo32 porous framework, and carrying out infiltration in a vacuum infiltration furnace at the infiltration temperature of 1250 ℃ for 100 minutes to obtain an infiltration method CuMo25 contact material;
the resistivity of the contact material tested by the infiltration method CuMo25 is reduced by 0.23 mu omega cm compared with the resistivity of 2.31 mu omega cm by the sintering method.
Example four
Weighing 10kg of CuMo37 mixed powder, adding 500g of 5 wt% ammonium oxalate solution, 5 wt% ammonium hydrogen oxalate solution, 5 wt% ammonium bicarbonate solution and 5 wt% ammonium carbonate solution, uniformly stirring, and sieving the stirred powder by using a 100-mesh stainless steel sieve to obtain CuMo powder particles wrapped by a foaming agent;
putting the screened powder into a stainless steel boat, transferring the stainless steel boat into a vacuum oven, heating the stainless steel boat to 60 ℃, preserving heat for 30 minutes, transferring the foamed powder and the stainless steel boat into an ammonia decomposition atmosphere sintering furnace, sintering the powder and the stainless steel boat at 500 ℃, and preserving heat for 120 minutes;
stirring the sintering-strengthened powder in a stirrer, heating the powder, spraying 2kg of 1 wt% paraffin-gasoline solution, completely wrapping the powder, and heating and stirring until the gasoline in the powder is dried;
sintering the powder-loaded corundum boat subjected to the calcined paraffin coating treatment under an ammonia decomposition atmosphere, wherein the sintering process comprises the steps of 500 ℃, 60 minutes, 700 ℃, 60 minutes, 900 ℃, 60 minutes, 1200 ℃ and 60 minutes, and after sintering, cooling, crushing and sieving by a 50-mesh sieve to obtain high-strength porous prefabricated CuMo37 powder with fluidity;
pressing porous prefabricated CuMo37 powder into a CuMo37 porous framework with the single weight of 5g, spraying 300-mesh alumina powder containing 12 wt% of silicon on the surface of the framework until the surface is completely covered, arranging a pure copper sheet with the single weight of 1.17g on the CuMo37 porous framework, and carrying out infiltration in a vacuum infiltration furnace at the infiltration temperature of 1200 ℃ for 60 minutes to obtain an infiltration method CuMo30 contact material;
the resistivity of the contact material tested by the infiltration method CuMo30 is reduced by 0.27 mu omega cm compared with the resistivity of 2.50 mu omega cm compared with the sintering method.
EXAMPLE five
Weighing 5kg of CuWC30 mixed powder, respectively adding 200g of 6 wt% ammonium oxalate solution and 6 wt% ammonium hydrogen oxalate solution, uniformly stirring, and sieving the stirred powder by using a 200-mesh stainless steel sieve to obtain CuWC powder particles coated by a foaming agent;
putting the screened powder into a graphite boat, transferring the graphite boat into a vacuum oven, heating the graphite boat to 100 ℃, preserving heat for 60 minutes, transferring the foamed powder and the graphite boat into a vacuum sintering furnace, sintering the graphite boat for 600 ℃, and preserving heat for 60 minutes;
stirring the sintering-strengthened powder in a stirrer, heating the powder, spraying 0.5kg of 4% paraffin-gasoline solution, completely wrapping the powder, and heating and stirring until the gasoline in the powder is dried;
loading the calcined paraffin coated powder into a boat, sintering at 450 ℃, 90 minutes, 650 ℃, 90 minutes, 850 ℃, 90 minutes and 1100 ℃, 90 minutes in a vacuum atmosphere, cooling, crushing and sieving with a 80-mesh sieve after sintering to obtain high-strength porous prefabricated CuWC30 powder with fluidity;
pressing porous prefabricated CuWC30 powder into a CuWC30 porous framework with the single weight of 6g, spraying 400-mesh alumina powder containing 10 wt% of silicon on the surface of the framework until the surface is completely covered, arranging pure copper sheets with the single weight of 3g on the CuWC30 porous framework, and carrying out infiltration in a vacuum infiltration furnace, wherein the infiltration temperature is 1100 ℃, and the infiltration time is 90 minutes to obtain an infiltration method CuWC20 contact material;
the resistivity of the contact material tested by the infiltration method CuWC20 is reduced by 0.27 mu omega cm compared with the resistivity of 2.43 mu omega cm compared with the sintering method by 2.16 mu omega cm.
EXAMPLE six
Weighing 5kg of CuWC33 mixed powder, respectively adding 600g of 6 wt% ammonium oxalate solution, uniformly stirring, and sieving the stirred powder by using a 100-mesh stainless steel sieve to obtain CuWC powder particles coated by a foaming agent;
putting the screened powder into a graphite boat, transferring the graphite boat into a vacuum oven, heating the graphite boat to 80 ℃, preserving heat for 50 minutes, transferring the foamed powder and the graphite boat into a vacuum sintering furnace, sintering the graphite boat for 700 ℃, and preserving heat for 60 minutes;
stirring the sintering-strengthened powder in a stirrer, heating the powder, spraying 0.8kg of 4% paraffin-gasoline solution, completely wrapping the powder, and heating and stirring until the gasoline in the powder is dried;
loading the calcined paraffin coated powder into a boat, sintering in a vacuum atmosphere, wherein the sintering process is 450 ℃, 80 minutes, 650 ℃, 80 minutes, 850 ℃, 80 minutes and 1100 ℃, 80 minutes, cooling, crushing and sieving with an 80-mesh sieve after sintering to obtain high-strength porous prefabricated CuWC33 powder with fluidity;
pressing porous prefabricated CuWC33 powder into a CuWC33 porous skeleton with the single weight of 6g, spraying 300-mesh silicon-containing 7 wt% alumina powder on the surface of the skeleton until the surface is completely covered, arranging a pure copper sheet with the single weight of 1.92g on the CuWC33 porous skeleton, and carrying out infiltration in a vacuum infiltration furnace at the infiltration temperature of 1180 ℃ for 90 minutes to obtain an infiltration method CuWC33 contact material;
the resistivity of the contact material tested by the infiltration method CuWC25 is reduced by 0.31 mu omega cm compared with the resistivity of 2.57 mu omega cm compared with the sintering method.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. A preparation method of a framework for an infiltration preparation process of a copper-based electric contact material is characterized by comprising the following steps of:
(1) foaming: adding a foaming agent into the copper-based mixed powder, uniformly stirring and sieving to obtain copper-based mixed powder particles wetted by the foaming agent, and heating and foaming the sieved copper-based mixed powder particles in an oven;
(2) solid-phase sintering and strengthening: solid-phase sintering the copper-based mixed powder particles foamed in the step (1) to form fixed pores inside the particles;
(3) packaging release agent: heating and stirring the copper-based mixed powder particles sintered and reinforced in the step (2) in a stirrer, and spraying a paraffin solution at the same time to wrap the powder by the paraffin and dry a solvent of the paraffin solution in the stirring process;
(4) powder liquid phase sintering: carrying out high-temperature liquid phase sintering on the copper-based mixed powder particles coated with paraffin in the step (3), and crushing and screening the sintered powder to obtain high-strength porous prefabricated powder with good fluidity;
(5) pressing: and pressing and molding the porous prefabricated powder into a framework.
2. The method of claim 1, wherein: the adding amount of the foaming agent in the step (1) is that the mass ratio of the effective components to the powder is 1: 100-1000, wherein the spraying amount of the paraffin solution in the step (3) is 1:100-1:500 according to the mass ratio of the paraffin to the powder.
3. The method of claim 1, wherein: the copper-based mixed powder contains 50-70 wt% of Cu, and the balance of one or a combination of W, WC and Mo.
4. The method of claim 1, wherein: the foaming agent is one or a combination of ammonium bicarbonate, ammonium carbonate, ammonium hydrogen oxalate and ammonium oxalate.
5. The method of claim 1, wherein: the powder screening process in the step (1) is a 100-mesh and 300-mesh screening process, and the foaming process after screening is as follows: the foaming temperature is 60-200 ℃, and the foaming time is 30-60 minutes.
6. The method of claim 1, wherein: the solid phase sintering process in the step (2) comprises the following steps: the sintering temperature is 500-800 ℃, the sintering time is 30-120 minutes, and the sintering atmosphere is reducing or vacuum atmosphere.
7. The method of claim 1, wherein: in the step (3), the heating temperature is 60-100 ℃, the paraffin content in the paraffin-containing solution is 1-10 wt%, and the solvent is gasoline.
8. The method of claim 1, wherein: the liquid phase sintering process in the step (4) comprises the following steps: a gradient sintering process, in particular to sintering at 400-500 ℃ for 60-120 minutes,
sintering at 600-700 deg.c for 60-120 min and at 800-900 deg.c for 60-120 min,
sintering at 1100-1300 deg.c for 60-120 min in reducing atmosphere or vacuum atmosphere.
9. A method for preparing a copper-based electric contact material based on a foaming infiltration process is characterized in that the method is based on the framework prepared by the method of any one of claims 1 to 8, pure copper sheets are added on the framework, silicon-containing corundum powder is sprayed on the framework, and the copper-based electric contact material is obtained by infiltration in an infiltration furnace.
10. A copper-based electrical contact material prepared according to the method of claim 9.
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