CN101537491B - Preparation method of copper-coated tungsten composite powder - Google Patents
Preparation method of copper-coated tungsten composite powder Download PDFInfo
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- CN101537491B CN101537491B CN2009100831131A CN200910083113A CN101537491B CN 101537491 B CN101537491 B CN 101537491B CN 2009100831131 A CN2009100831131 A CN 2009100831131A CN 200910083113 A CN200910083113 A CN 200910083113A CN 101537491 B CN101537491 B CN 101537491B
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Abstract
The invention discloses a preparation method of copper-coated tungsten composite powder, belonging to the technical field of powder metallurgy. Corresponding tungsten powder and blue vitriod are employed according to the weight ratio of composite powder to be prepared and the tungsten powder is pre-treated; copper sulphate and seignette sol are dissolved into solution; bipyridine is added and NaOH is used to adjust pH value to 12-14; an appropriate amount of formaldehyde solution and the tungsten powder are added; the mixture is heated and then stirred continuously in constant-temperature bathing at 30-60 DEG C until the tungsten powder is red; the tungsten powder is washed, dried, reduced and annealed, thereby obtaining copper-coated tungsten composite powder. The preparation method of copper-coated tungsten composite powder has wide application range and is applicable to tungsten-powder coating coppers with different finenesses and shapes. The preparation method of copper-coated tungsten composite powder prepares copper-coated tungsten composite powder in different content ratios according to different requirements. The copper-coated tungsten composite powder obtained by the method of the invention has excellent sintering activity, thereby improving the combination property of tungsten copper alloy.
Description
Technical field
The invention belongs to powder metallurgical technology, relate to a kind of preparation method who produces the copper-coated tungsten composite powder that tungsten-copper alloy uses particularly.
Background technology
Tungsten-copper alloy be a kind of by body-centered cubic structure tungsten and the copper of face-centred cubic structure form neither mutually solid solution do not form the two-phase line and staff control of intermetallic compound again, be commonly called pseudo-alloy.Therefore, it had both had the characteristics such as high strength, high rigidity, low-expansion coefficient of tungsten, had the characteristics such as high-ductility, favorable conductive thermal conductivity of copper simultaneously again.This distinctive combination property makes tungsten-copper alloy obtain using widely in contact material and electrode material.
When preparation W-Cu alloy, common production technology for tungsten powder and copper powder are mixed in proportion, shaping, sintering, following process, or adopt tungsten powder, copper powder to be formed separately, copper pressed compact and tungsten pressed compact are overlayed the infiltration technology of 1200 ℃ of high temperature～1300 ℃ of following sintering etc.In this conventional art,, no matter be that liquid-phase sintering or solid-phase sintering all are difficult to obtain high fine and close tungsten-copper alloy therefore because W-Cu liquid phase angle of wetting is non-vanishing and W-Cu does not dissolve again mutually.Though repressing and re-sintering or subsequent thermal processing can improve product density, cost increases, and efficient reduces.
Along with the development of microelectronics information technology, in large scale integrated circuit and HIGH-POWERED MICROWAVES device, the W-Cu composite has purposes widely as electronic package material such as substrate, connector and heat dissipation element and heat sink material.The Tungsten-copper Composites that is applied to microelectric technique requires to have very high performance: the density height, and leak rate is low, and conduction, heat conductivility are good, and thermal diffusivity is good.And adopt when carrying out liquid-phase sintering behind the mixed-powder compacting blank again and obtaining the high tungsten-copper alloy of W content, often because tungsten not dissolving and cause final porous in liquid phase copper, be difficult to densified sintering product, especially the volume fraction at tungsten generally only is 92%～95% above 65% o'clock relative density the highest.Cause tungsten-copper alloy intensity, conduction, heat conductivility low thus, the leak rate height is difficult to satisfy the requirement of modern industry.For the sintered density of the tungsten-copper composite material that improves high W content, a lot of researchers have adopted the method for adding sintering aid to carry out activated sintering, but the adding of activator has very big infringement to thermal conductivity, is not suitable for heat sink material.
When powder metallurgical technique prepared tungsten-copper alloy, the original mixed state of powder and batch mixing uniformity had directly had influence on the preparation technology of alloy, the porosity of alloy and the existence of micro-crack, had also had influence on the performance of alloy simultaneously.Therefore obtain the tungsten copper mixed-powder that is evenly distributed the application of material is had fundamental influence.
In order to improve the tungsten copper powder mixing uniformity and to improve powder sintered activity, aspect the preparation W-Cu composite powder, mechanical alloying method, oxide co-reducing process and electroless plating method have appearred at present.
Summary of the invention
It is poor to the objective of the invention is to solve contaminated environment, working condition that present nitrate decomposition technique (chemical batch mixing method) exists, the bad problem of the machinery bad and powder sintered wellability of batch mixing uniformity adopts the mode of tungsten powder surface electroless copper to improve the agglutinating property of tungsten-copper alloy, the density that improves agglomerated material and other material property.
A kind of chemical plating prepares the method for copper cladding tungsten composite powder, and concrete operating procedure is as follows:
Step 1: according to tungsten proportion in the W-Cu composite powder, the quality of getting corresponding tungsten powder was at first soaked 10 minutes with 10g/LNaOH, remove upper solution then, and use washed with de-ionized water, and soaked tungsten powder 20 minutes with 10%HCl again, remove upper solution then and clean tungsten powder;
Step 2: according to the required weight of copper in the class composite W-Cu powder, take by weighing 3.89 times of cupric sulfate pentahydrates of Cu weight, and use deionized water dissolving, be made into the copper-bath of 13-15g/L;
Step 3: get sodium potassium tartrate tetrahydrate, use deionized water dissolving, then copper-bath is joined under stirring condition in the potassium sodium tartrate solution slowly, the concentration of control solution mesotartaric acid potassium sodium is 52-65g/L, obtains light blue suspension;
Step 4: be added in the suspension that joins gained in the step 3 under the stirring condition after getting NaOH dissolving, solution becomes navy blue, and adjusts pH value in the 12-14 scope, and adding second bipyridine this moment, to control its concentration be 0.01-0.03g/L;
Step 5: it is 37%-40% formaldehyde that the mass concentration of the 1.5%-2% of required total solution weight is answered in negate, adds in the solution of step 4 gained, and adds tungsten powder;
Step 6: the muddy liquid of step 5 gained is heated in 30-60 ℃ of water bath with thermostatic control, and constantly stir, tungsten powder is suspended in the solution, redden to tungsten powder, after the clarification of muddy liquid upper strata, stop heating and stir with agitator;
Step 7: the muddy liquid after will plating is after static 20 minutes, removes upper solution, and with washed with de-ionized water W-Cu composite powder 3 times, drying in drying box then;
Step 8: the powder after will drying reduced 1 hour in 300-400 ℃ of hydrogen furnace, promptly obtained copper-coated tungsten composite powder.
The inventive method technology is simple, and accommodation is wide.The copper-coated tungsten composite powder of the present invention's preparation has following advantage: coating thickness is even, and coating thickness can be adjusted, and can prepare the W-Cu composite powder of different content according to demand; The big or small pattern of tungsten particle is unrestricted, can coat thick tungsten powder (tens microns), thin tungsten powder (several microns), spherical tungsten powder and sheet tungsten powder; The coating oxygen content is few, free from admixture etc.The copper-coated tungsten composite powder of the present invention's preparation has high sintering activity, can improve the structural homogenity of tungsten-copper alloy, and combination properties such as the heat conductivility of raising tungsten-copper alloy, mechanical property play important effect to the application of tungsten copper powder and alloy.
Description of drawings
Fig. 1 is original tungsten powder SEM pattern;
Fig. 2 is a plating back copper clad tungsten powder SEM pattern;
Fig. 3 is the back copper-clad tungsten powder particles SEM pattern of plating;
Fig. 4 is the back copper-clad tungsten powder particles cross-section photograph of plating.
The specific embodiment
Example 1
Preparation 100gW-10Cu composite powder.Get 30 μ m tungsten powder 90g.At first soaked 10 minutes, remove upper solution then, and use washed with de-ionized water with 10g/LNaOH.Soaked tungsten powder 20 minutes with 10%HCl again, remove upper solution then and clean tungsten powder.
Get the 38.9g cupric sulfate pentahydrate, and use deionized water dissolving, be made into the copper-bath of 13g/L.Get the sodium potassium tartrate tetrahydrate of 156g, use deionized water dissolving.Then copper-bath is joined in the potassium sodium tartrate solution under stirring condition slowly, obtain light blue suspension.Get NaOH dissolving back this moment and add in the above-mentioned light blue suspension, solution becomes navy blue, and adjusting pH value is 12.And the second bipyridine of adding 0.03g.Join tungsten powder and 60ml formaldehyde in the above-mentioned navy blue solution this moment.In 30 ℃ of waters bath with thermostatic control, heat, and constantly stir, tungsten powder is suspended in the solution with agitator.Redden to tungsten powder, after the clarification of muddy liquid upper strata, stop heating and stir.With the muddy liquid after static 20 minutes after the plating, remove upper solution, and with washed with de-ionized water W-Cu composite powder 3 times, drying in drying box then, and carried out hydrogen annealing 1 hour at 300 ℃, promptly obtain copper-coated tungsten composite powder
Example two
Preparation 200gW-10Cu composite powder.Get 30 μ m tungsten powder 180g.At first soaked 10 minutes, remove upper solution then, and use washed with de-ionized water with 10g/LNaOH.Soaked tungsten powder 20 minutes with 10%HCl again, remove upper solution then and clean tungsten powder.
Get the 77.8g cupric sulfate pentahydrate, and use deionized water dissolving, be made into the copper-bath of 13.5g/L.Get the sodium potassium tartrate tetrahydrate of 311g, use deionized water dissolving.Then copper-bath is joined in the potassium sodium tartrate solution under stirring condition slowly, obtain light blue suspension.Get NaOH dissolving back this moment and add in the above-mentioned light blue suspension, solution becomes navy blue, adjusts pH value in 12.5 scopes.And the second bipyridine of adding 0.11g.Join tungsten powder and 86.4ml formaldehyde in the above-mentioned navy blue solution this moment.In 35 ℃ of waters bath with thermostatic control, heat, and constantly stir, tungsten powder is suspended in the solution with agitator.Redden to tungsten powder, after the clarification of muddy liquid upper strata, stop heating and stir.With the muddy liquid after static 20 minutes after the plating, remove upper solution, and with washed with de-ionized water W-Cu composite powder 3 times, drying in drying box then, and carried out hydrogen annealing 1 hour at 320 ℃, promptly obtain copper-coated tungsten composite powder
Example three
Preparation 100gW-15Cu composite powder.Get 10 μ m tungsten powder 85g.At first soaked 10 minutes, remove upper solution then, and use washed with de-ionized water with 10g/LNaOH.Soaked tungsten powder 20 minutes with 10%HCl again, remove upper solution then and clean tungsten powder.
Get the 58.35g cupric sulfate pentahydrate, and use deionized water dissolving, be made into the copper-bath of 14g/L.Get the sodium potassium tartrate tetrahydrate of 233g, use deionized water dissolving.Then copper-bath is joined in the potassium sodium tartrate solution under stirring condition slowly, obtain light blue suspension.Get NaOH dissolving back this moment and add in the above-mentioned light blue suspension, solution becomes navy blue, and adjusting pH value is 13.And the second bipyridine of adding 0.12g.Join tungsten powder and 75.1ml formaldehyde in the above-mentioned navy blue solution this moment.In 40 ℃ of waters bath with thermostatic control, heat, and constantly stir, tungsten powder is suspended in the solution with agitator.Redden to tungsten powder, after the clarification of muddy liquid upper strata, stop heating and stir.With the muddy liquid after static 20 minutes after the plating, remove upper solution, and with washed with de-ionized water W-Cu composite powder 3 times, drying in drying box then, and carried out hydrogen annealing 1 hour at 450 ℃, promptly obtain copper-coated tungsten composite powder
Example four
Preparation 200gW-15Cu composite powder.Get 3 μ m tungsten powder 85g.At first soaked 10 minutes, remove upper solution then, and use washed with de-ionized water with 10g/LNaOH.Soaked tungsten powder 20 minutes with 17%HCl again, remove upper solution then and clean tungsten powder.
Get the 116.7g cupric sulfate pentahydrate, and use deionized water dissolving, be made into the copper-bath of 14.5g/L.Get the sodium potassium tartrate tetrahydrate of 480g, use deionized water dissolving.Then copper-bath is joined in the potassium sodium tartrate solution under stirring condition slowly, obtain light blue suspension.Get NaOH dissolving back this moment and add in the above-mentioned light blue suspension, solution becomes navy blue, and adjusting pH value is 13.5.And the second bipyridine of adding 0.24g.Join tungsten powder and 160ml formaldehyde in the above-mentioned navy blue solution this moment.In 50 ℃ of waters bath with thermostatic control, heat, and constantly stir, tungsten powder is suspended in the solution with agitator.Redden to tungsten powder, after the clarification of muddy liquid upper strata, stop heating and stir.With the muddy liquid after static 20 minutes after the plating, remove upper solution, and with washed with de-ionized water W-Cu composite powder 3 times, drying in drying box then, and carried out hydrogen annealing 1 hour at 380 ℃, promptly obtain copper-coated tungsten composite powder.
Example five
Preparation 500gW-20Cu composite powder.Get 50 μ m tungsten powder 400g.At first soaked 10 minutes, remove upper solution then, and use washed with de-ionized water with 10g/LNaOH.Soaked tungsten powder 20 minutes with 10%HCl again, remove upper solution then and clean tungsten powder.
Get the 389g cupric sulfate pentahydrate, and use deionized water dissolving, be made into the copper-bath of 15g/L.Get the sodium potassium tartrate tetrahydrate of 1690g, use deionized water dissolving.Then copper-bath is joined in the potassium sodium tartrate solution under stirring condition slowly, obtain light blue suspension.Get NaOH dissolving back this moment and add in the above-mentioned light blue suspension, solution becomes navy blue, and adjusting the pH value is 14.And the second bipyridine of adding 0.52g.Join tungsten powder and 416ml formaldehyde in the above-mentioned navy blue solution this moment.In 60 ℃ of waters bath with thermostatic control, heat, and constantly stir, tungsten powder is suspended in the solution with agitator.Redden to tungsten powder, after the clarification of muddy liquid upper strata, stop heating and stir.With the muddy liquid after static 20 minutes after the plating, remove upper solution, and with washed with de-ionized water W-Cu composite powder 3 times, drying in drying box then, and carried out hydrogen annealing 1 hour at 400 ℃, promptly obtain copper-coated tungsten composite powder.
Claims (1)
1. a chemical plating prepares the method for copper cladding tungsten composite powder, it is characterized in that concrete operating procedure is as follows:
Step 1: according to tungsten proportion in the W-Cu composite powder, the quality of getting corresponding tungsten powder was at first soaked 10 minutes with 10g/LNaOH, remove upper solution then, and use washed with de-ionized water, and soaked tungsten powder 20 minutes with 10%HCl again, remove upper solution then and clean tungsten powder;
Step 2: according to the required weight of copper in the class composite W-Cu powder, take by weighing 3.89 times of cupric sulfate pentahydrates of Cu weight, and use deionized water dissolving, be made into the copper-bath of 13-15g/L;
Step 3: get sodium potassium tartrate tetrahydrate, use deionized water dissolving, then copper-bath is joined under stirring condition in the potassium sodium tartrate solution slowly, the concentration of control solution mesotartaric acid potassium sodium is 52-65g/L, obtains light blue suspension;
Step 4: get NaOH dissolving back and join in the suspension of gained in the step 3 under stirring condition, solution becomes navy blue, and adjusts pH value in the 12-14 scope, and adding second bipyridine this moment, to control its concentration be 0.01-0.03g/L;
Step 5: it is 37%-40% formaldehyde that the mass concentration of the 1.5%-2% of required total solution weight is answered in negate, adds in the solution of step 4 gained, and adds tungsten powder;
Step 6: the muddy liquid of step 5 gained is heated in 30-60 ℃ of water bath with thermostatic control, and constantly stir, tungsten powder is suspended in the solution, redden to tungsten powder, after the clarification of muddy liquid upper strata, stop heating and stir with agitator;
Step 7: the muddy liquid after will plating is after static 20 minutes, removes upper solution, and with washed with de-ionized water W-Cu composite powder 3 times, drying in drying box then;
Step 8: the powder after will drying reduced 1 hour in 300-400 ℃ of hydrogen furnace, promptly obtained copper-coated tungsten composite powder.
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