CN109093111A - A kind of preparation method of copper-tungsten - Google Patents

Abstract

The invention discloses a kind of preparation methods of copper-tungsten, include the following steps；Step 1: the tungsten powder of preparation surface deposit cobalt: the content of cobalt is 0.55%-1.11%, and surplus is tungsten；Step 2: cupric ammine complex is prepared；Step 3: preparing the tungsten copper powder of copper-depositing on surface；Step 4: molding；Step 5: infiltration, cleaning；The weight ratio of tungsten copper nickel is set 100:(5-6 by the present invention): (0.55-1.1), tungsten average particle size are 2-6um；And maximum particle size≤20 μm, minimum particle size >=0.1 μm；Cobalt is derived from cobalt acetate solution, and the pure nitric acid by copper powder with concentration for 60%-65%, which dissolves, is made cupric ammine complex；Preparation method is simple, simple process, easy to operate, and it is high to stablize arc resistant ablation property according to the Tungsten-copper Composites performance that this method obtains, and the high size of W content is big and has thin-walled.

Description

A kind of preparation method of copper-tungsten

Technical field

High, arc resistance that the present invention relates to the field of copper-tungsten more particularly to a kind of W contents can it is good, size is big and has The preparation method of the copper-tungsten of thin-walled portion.

Background technique

W-Cu electrical contact material is by high-melting-point, the tungsten of high rigidity and highly conductive, the false conjunction that the copper of high thermal conductivity is constituted Gold；With the high speed development of modernization construction, high voltage power transmission power transformation network load increasingly increases, and device for switching is towards higher electricity Pressure, larger capacity direction is developed；Traditional high pressure W-Cu electrical contact material, under high voltage, high current effect, arc erosion makes Contact surface generates serious erosion and resists and cause premature failure, is no longer satisfied demand；Therefore, tungsten can be significantly improved by finding one kind The preparation method of copper electrical contact material performance, just seems necessary.

Summary of the invention

It is an object of the present invention to provide a kind of preparation method is simple, the preparation method of easy to operate copper-tungsten is solved The above technical problem.

In order to achieve the above technical purposes, reach above-mentioned technical requirements, the technical scheme adopted by the invention is that: it is a kind of The preparation method of copper-tungsten, it is characterised in that: include the following steps；

Step 1: the tungsten powder of preparation surface deposit cobalt: the content of cobalt is 0.55%-1.11%, and surplus is tungsten；The tungsten is averaged grain Degree is 2-6um；And maximum particle size≤20 μm, minimum particle size >=0.1 μm；49.5kg tungsten powder is taken, the cobalt containing 0.5kg is added thereto Cobalt acetate solution, with even, drying, 150 DEG C of drying temperature <, drying time is 14-16 hours, and obtained powder crosses 250 targets Then quasi- sieve carries out 900-1050 DEG C, restores in 1-3 hours hydrogen streams, after 250 meshes after reduction, the tungsten-cobalt of acquisition is mixed Powder is spare；

Step 2: preparing cupric ammine complex: the weight ratio of tungsten copper nickel is 100:(5-6): (0.55-1.1) measures copper powder, with The pure nitric acid that concentration is 60%-65% dissolves, and the weight ratio of copper and nitric acid is 1:(3.0-3.15)；Copper ammonia complexation is made after 10 hours Object solution, with special pH test paper, control terminal pH value is 10-12, and filtering is spare；

Step 3: preparing the tungsten copper powder of copper-depositing on surface: again by gained tungsten-cobalt powder in step 1, be transferred to a mixing bowl, addition go from The ratio of sub- water, tungsten-cobalt powder and ionized water is 1:(0.5-1), then combine and hydrazine hydrate and ammonium hydroxide is added, 50kg tungsten-cobalt is mixed It closes powder and 500ml hydrazine hydrate is added, 2000ml ammonium hydroxide is stirred with the revolving speed lower than 200 revs/min, stirred to realize induction Mix time < 2 hours；Then the cupric ammine complex solution in step 2 is transferred to a mixing bowl, mixing speed be 500-3000 turn/ Minute, and hydrazine hydrate is slowly added to be less than the speed of 100ml per minute to control terminal, copper-clad tungsten is obtained after completion of the reaction Co composite powder, the copper of the copper-clad tungsten-cobalt composite powder with a thickness of 1-10 μm, adopt be washed with deionized water to the greatest extent, control deionized water Conductivity < 2 it is micro- western per cm, then filtered, dry, 100 DEG C of drying temperature <；Copper-clad tungsten-cobalt after drying is compound Powder restores in 200-400 DEG C of hydrogen stream, crosses 150 meshes, it is spare to obtain powder；

Step 4: by step 3 obtain copper-clad tungsten-cobalt powder by shape of product form, the powder have good mouldability with Mobility produces wall thickness in the thin-wall part of 1mm or more；

Step 5: molding pressure embryo is entered furnace infiltration, temperature is risen into 900 DEG C of reduction 30-90 minutes, then be warming up to 1150-1300 DEG C carry out infiltration 1-3 hours；It is cleaned after coming out of the stove.

Beneficial effects of the present invention；A kind of preparation method of copper-tungsten, the weight ratio of tungsten copper nickel are set as 100:(5- 6): (0.55-1.1), tungsten average particle size are 2-6um；And maximum particle size≤20 μm, minimum particle size >=0.1 μm；Cobalt is derived from cobalt acetate Solution, the pure nitric acid by copper powder with concentration for 60%-65%, which dissolves, is made cupric ammine complex；Preparation method is simple, simple process, holds Easy to operate, it is high that the Tungsten-copper Composites performance obtained according to this method stablizes arc resistant ablation property, and the high size of W content it is big and There is thin-walled.

Specific embodiment

In order to be more clear goal of the invention of the invention, technical solution and its advantageous effects, below in conjunction with specific Embodiment, the present invention will be described in further detail；

A kind of preparation method of copper-tungsten, it is characterised in that: include the following steps；

Step 1: the tungsten powder of preparation surface deposit cobalt: the content of cobalt is 0.55%-1.11%, and surplus is tungsten；The tungsten is averaged grain Degree is 2-6um；And maximum particle size≤20 μm, minimum particle size >=0.1 μm；49.5kg tungsten powder is taken, the cobalt containing 0.5kg is added thereto Cobalt acetate solution, with even, drying, 150 DEG C of drying temperature <, drying time is 14-16 hours, and obtained powder crosses 250 targets Then quasi- sieve carries out 900-1050 DEG C, restores in 1-3 hours hydrogen streams, after 250 meshes after reduction, the tungsten-cobalt of acquisition is mixed Powder is spare；

Step 2: preparing cupric ammine complex: the weight ratio of tungsten copper nickel is 100:(5-6): (0.55-1.1) measures copper powder, with The weight ratio of pure nitric acid dissolution, copper and nitric acid is 1:(3.0-3.15)；Cupric ammine complex solution is made after 10 hours, with accurate PH Test paper, control terminal pH value are 10-12, and filtering is spare；

Step 3: preparing the tungsten copper powder of copper-depositing on surface: again by gained tungsten-cobalt powder in step 1, be transferred to a mixing bowl, addition go from The ratio of sub- water, tungsten-cobalt powder and ionized water is 1:(0.5-1), then combine and hydrazine hydrate and ammonium hydroxide is added, 50kg tungsten-cobalt is mixed It closes powder and 500ml hydrazine hydrate is added, 2000ml ammonium hydroxide is stirred with the revolving speed lower than 200 revs/min, stirred to realize induction Mix time < 2 hours；Then the cupric ammine complex solution in step 2 is transferred to a mixing bowl, mixing speed be 500-3000 turn/ Minute, and hydrazine hydrate is slowly added to be less than the speed of 100ml per minute to control terminal, copper-clad tungsten is obtained after completion of the reaction Co composite powder, the copper of the copper-clad tungsten-cobalt composite powder with a thickness of 1-10 μm, adopt be washed with deionized water to the greatest extent, control deionized water Conductivity < 2 it is micro- western per cm, then filtered, dry, 100 DEG C of drying temperature <；Copper-clad tungsten-cobalt after drying is compound Powder restores in 200-400 DEG C of hydrogen stream, crosses 150 meshes, it is spare to obtain powder；

Step 4: by step 3 obtain copper-clad tungsten-cobalt powder by shape of product form, the powder have good mouldability with Mobility produces wall thickness in the thin-wall part of 1mm or more；

Step 5: molding pressure embryo is entered furnace infiltration, temperature is risen into 900 DEG C of reduction 30-90 minutes, then be warming up to 1150-1300 DEG C carry out infiltration 1-3 hours；It is cleaned after coming out of the stove.

Specific implementation of the invention:

Case 1: taking 99.45kg tungsten powder, and the cobalt acetate solution of the cobalt containing 0.55kg is added thereto, with even, drying, drying temperature < 150 DEG C, drying time is 14 hours, and obtained powder crosses 250 mesh standard sieves, then carries out 900 DEG C, goes back in 1 hour hydrogen stream Original, after 250 meshes after reduction, the 50kg tungsten-cobalt mixed powder of acquisition is spare；4.97kg copper powder is weighed, with the pure nitric acid of 14.92kg Dissolution, was made cupric ammine complex solution after 10 hours, and with special pH test paper, controlling terminal pH value is 10, and filtering is spare；Again will 100kg tungsten-cobalt powder is transferred to a mixing bowl, and 50kg deionized water is added, then combines and 1000ml hydrazine hydrate and ammonium hydroxide is added, 4000ml ammonium hydroxide is stirred, mixing time < 2 hours with realizing induction with the revolving speed lower than 200 revs/min；It then will system Standby cupric ammine complex solution is transferred to a mixing bowl, and mixing speed is 500 revs/min, and slow to be less than the speed of 100ml per minute The slow hydrazine hydrate that is added obtains copper-clad tungsten-cobalt composite powder to control terminal after completion of the reaction, the copper-clad tungsten-cobalt composite powder Copper with a thickness of 1 μm, adopt be washed with deionized water to the greatest extent, the conductivity < 2 for controlling deionized water is micro- western per cm, is then taken out Filter, drying, 100 DEG C of drying temperature <；Copper-clad tungsten-cobalt composite powder after drying restores in 200 DEG C of hydrogen streams, crosses 150 mesh Sieve, it is spare to obtain copper-clad tungsten-cobalt composite powder；Then copper-clad tungsten-cobalt powder is formed by shape of product, which has good molding Property and mobility, produce wall thickness in the thin-wall part of 1mm or more；Molding pressure embryo is entered into furnace infiltration, temperature is risen to 900 DEG C also It is 30 minutes former, then it is warming up to 1150 DEG C of progress infiltration 1 hour；Cleaning obtains the large-sized thin wall type copper tungsten conjunction of high tungsten after coming out of the stove Gold.

Case 2: taking 98.89kg tungsten powder, and the cobalt acetate solution of the cobalt containing 1.11kg is added thereto, with even, drying, drying temperature 150 DEG C of < of degree, drying time are 16 hours, and obtained powder crosses 250 mesh standard sieves, then carries out 1050 DEG C, 3 hours hydrogen streams Middle reduction, after 250 meshes after reduction, the 100kg tungsten-cobalt mixed powder of acquisition is spare；5.93kg copper powder is weighed, it is pure with 18.69kg Nitric acid dissolution, was made cupric ammine complex solution after 10 hours, and with special pH test paper, controlling terminal pH value is 10, and filtering is spare； 50kg tungsten-cobalt powder is transferred to a mixing bowl again, 50kg ionized water is removed in addition, then combines and 1000ml hydrazine hydrate and ammonium hydroxide is added, 4000ml ammonium hydroxide is stirred, mixing time < 2 hours with realizing induction with the revolving speed lower than 200 revs/min；It then will system Standby cupric ammine complex solution is transferred to a mixing bowl, and mixing speed is 500 revs/min, and slow to be less than the speed of 100ml per minute The slow hydrazine hydrate that is added obtains copper-clad tungsten-cobalt composite powder to control terminal after completion of the reaction, the copper-clad tungsten-cobalt composite powder Copper with a thickness of 10 μm, adopt be washed with deionized water to the greatest extent, the conductivity < 2 for controlling deionized water is micro- western per cm, is then taken out Filter, drying, 100 DEG C of drying temperature <；Copper-clad tungsten-cobalt composite powder after drying restores in 400 DEG C of hydrogen streams, crosses 150 mesh Sieve, it is spare to obtain copper-clad tungsten-cobalt composite powder；Then copper-clad tungsten-cobalt powder is formed by shape of product, which has good molding Property and mobility, produce wall thickness in the thin-wall part of 1mm or more；Molding pressure embryo is entered into furnace infiltration, temperature is risen to 900 DEG C also It is 90 minutes former, then it is warming up to 1300 DEG C of progress infiltration 3 hours；Cleaning obtains the large-sized thin wall type copper tungsten conjunction of high tungsten after coming out of the stove Gold.

Case 3: taking 99kg tungsten powder, and the cobalt acetate solution of the cobalt containing 1kg is added thereto, with even, drying, drying temperature < 150 DEG C, drying time is 15 hours, and obtained powder crosses 250 mesh standard sieves, then carries out 950 DEG C, goes back in 2 hours hydrogen streams Original, after 250 meshes after reduction, the 50kg tungsten-cobalt mixed powder of acquisition is spare；4.95kg copper powder is weighed, with the pure nitric acid of 14.85kg Dissolution, was made cupric ammine complex solution after 10 hours, and with special pH test paper, controlling terminal pH value is 10, and filtering is spare；Again will 100kg tungsten-cobalt powder is transferred to a mixing bowl, and 50kg ionized water is removed in addition, then combines and 1000ml hydrazine hydrate and ammonium hydroxide is added, 4000ml ammonium hydroxide is stirred, mixing time < 2 hours with realizing induction with the revolving speed lower than 200 revs/min；It then will system Standby cupric ammine complex solution is transferred to a mixing bowl, and mixing speed is 500 revs/min, and slow to be less than the speed of 100ml per minute The slow hydrazine hydrate that is added obtains copper-clad tungsten-cobalt composite powder to control terminal after completion of the reaction, the copper-clad tungsten-cobalt composite powder Copper with a thickness of 8 μm, adopt be washed with deionized water to the greatest extent, the conductivity < 2 for controlling deionized water is micro- western per cm, is then taken out Filter, drying, 100 DEG C of drying temperature <；Copper-clad tungsten-cobalt composite powder after drying restores in 300 DEG C of hydrogen streams, crosses 150 mesh Sieve, it is spare to obtain copper-clad tungsten-cobalt composite powder；Then copper-clad tungsten-cobalt powder is formed by shape of product, which has good molding Property and mobility, produce wall thickness in the thin-wall part of 1mm or more；Molding pressure embryo is entered into furnace infiltration, temperature is risen to 900 DEG C also It is 60 minutes former, then it is warming up to 1200 DEG C of progress infiltration 2 hours；Cleaning obtains the large-sized thin wall type copper tungsten conjunction of high tungsten after coming out of the stove Gold.

Above-described embodiment is only intended to clearly illustrate description made by the present invention, and does not limit the embodiments, To those of ordinary skill in the art, other various forms of variations or change can also be made on the basis of the above description Dynamic, there is no necessity and possibility to exhaust all the enbodiments, and the obvious variation or change thus amplified out It is dynamic to be still in the protection scope of this invention.

Claims (1)

1. a kind of preparation method of copper-tungsten, it is characterised in that: include the following steps；

Step 1: the tungsten powder of preparation surface deposit cobalt: the content of cobalt is 0.55%-1.11%, and surplus is tungsten；The tungsten is averaged grain Degree is 2-6um；And maximum particle size≤20 μm, minimum particle size >=0.1 μm；49.5kg tungsten powder is taken, the cobalt containing 0.5kg is added thereto Cobalt acetate solution, with even, drying, 150 DEG C of drying temperature <, drying time is 14-16 hours, and obtained powder crosses 250 targets Then quasi- sieve carries out 900-1050 DEG C, restores in 1-3 hours hydrogen streams, after 250 meshes after reduction, the tungsten-cobalt of acquisition is mixed Powder is spare；

Step 2: preparing cupric ammine complex: the weight ratio of tungsten copper nickel is 100:(5-6): (0.55-1.1) measures copper powder, with The weight ratio of pure nitric acid dissolution, copper and nitric acid is 1:(3.0-3.15)；Cupric ammine complex solution is made after 10 hours, with accurate PH Test paper, control terminal pH value are 10-12, and filtering is spare；

Step 3: preparing the tungsten copper powder of copper-depositing on surface: again by gained tungsten-cobalt powder in step 1, be transferred to a mixing bowl, addition go from The ratio of sub- water, tungsten-cobalt powder and ionized water is 1:(0.5-1), then combine addition hydrazine hydrate and ammonium hydroxide and induced with realizing, 500ml hydrazine hydrate is added in 50kg tungsten-cobalt mixed powder, and 2000ml ammonium hydroxide is stirred with the revolving speed lower than 200 revs/min, stirred Mix time < 2 hours；Then the cupric ammine complex solution in step 2 is transferred to a mixing bowl, mixing speed be 500-3000 turn/ Minute, and it is slowly added to hydrazine hydrate again to be less than the speed of 100ml per minute, to control reaction end, after completion of the reaction Obtain copper-clad tungsten-cobalt composite powder, the copper of the copper-clad tungsten-cobalt composite powder with a thickness of 1-10 μm, adopt be washed with deionized water to the greatest extent, control The conductivity < 2 of deionized water processed is micro- western per cm, is then filtered, drying, and 100 DEG C of drying temperature <；Copper after drying Packet tungsten-cobalt composite powder restores in 200-400 DEG C of hydrogen stream, crosses 150 meshes, it is spare to obtain powder；

Step 4: by step 3 obtain copper-clad tungsten-cobalt powder by shape of product form, the powder have good mouldability with Mobility produces wall thickness in the thin-wall part of 1mm or more；

Step 5: molding pressure embryo is entered furnace infiltration, temperature is risen into 900 DEG C of reduction 30-90 minutes, then be warming up to 1150-1300 DEG C carry out infiltration 1-3 hours；It is cleaned after coming out of the stove.