CN104226978B - The application in metal powder metallurgy molding of a kind of polyvinyl alcohol water solution - Google Patents
The application in metal powder metallurgy molding of a kind of polyvinyl alcohol water solution Download PDFInfo
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- CN104226978B CN104226978B CN201410226428.8A CN201410226428A CN104226978B CN 104226978 B CN104226978 B CN 104226978B CN 201410226428 A CN201410226428 A CN 201410226428A CN 104226978 B CN104226978 B CN 104226978B
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Abstract
The invention discloses the application in metal powder metallurgy molding of a kind of polyvinyl alcohol water solution, the mass percent concentration of described polyvinyl alcohol water solution is 5～20%, and described metal dust includes one or more in tungsten, molybdenum, nickel, copper and ferrum；Described polyvinyl alcohol water solution is (0.5～5) with the mass ratio of described metal dust: 100.The polyvinyl alcohol water solution of the present invention is the most volatile; nonpoisonous and tasteless, pollution-free; use the problem that polyvinyl alcohol water solution can effectively reduce, as the adhesive in metal powder metallurgy, the product quality inhomogeneities that volatile type adhesive causes; directly slough with stove during follow-up sintering simultaneously and new degumming equipment and Degumming Procedures need not be increased; both protect environment, decrease pollution; reduce again cost, the stability of product quality is increased guarantee simultaneously.
Description
Technical field
The present invention relates to metal powder metallurgy field, particularly relate to a kind of polyvinyl alcohol water solution at metal powder
Application in the metallurgical molding in end.
Background technology
Current tungsten base high-specific-gravity alloy, the powdered metal molding procedure of molybdenum alloy mainly make recruitment
The mixture of industry wax or ethanol and glycerol is as adhesive.But industrial wax is at the glue as molding procedure
After stick, need when follow-up sintering operation to use vacuum dewaxing furnace can remove composition therein, its work
Skill operation length, cost are high.And the mixture of ethanol and glycerol as adhesive time, ethanol therein is easily
Volatilization cause environment partial contamination and and the blank density unevenness made, this gives follow-up pressure processing
Causing suitable unstability, yield rate reduces.
Summary of the invention
The technical problem to be solved is to overcome existing tungsten base high-specific-gravity alloy, molybdenum to close
The adhesive that gold uses in forming process can cause environmental pollution and the blank density unevenness made, product
The defect of product unstable properties, it is provided that a kind of polyvinyl alcohol water solution is in metal powder metallurgy molding
Application.Polyvinyl alcohol (PVA) aqueous solution of the present invention is the most volatile, nonpoisonous and tasteless, pollution-free, makes
Volatile type glue can be effectively reduced as the adhesive in metal powder metallurgy with polyvinyl alcohol water solution
The problem of the product quality inhomogeneities that stick causes, directly sloughs with stove during follow-up sintering simultaneously
And new degumming equipment and Degumming Procedures need not be increased, both protect environment, decreased pollution, lowered again
Cost, increases guarantee to the stability of product quality simultaneously.
The present invention is to solve above-mentioned technical problem by the following technical programs:
The invention provides the application in metal powder metallurgy molding of a kind of polyvinyl alcohol water solution, described
The mass percent concentration of polyvinyl alcohol water solution be 5～20%, described metal dust include tungsten, molybdenum,
One or more in nickel, copper and ferrum；Described polyvinyl alcohol water solution and the matter of described metal dust
Amount ratio is (0.5～5): 100.
Wherein, described polyvinyl alcohol can be various polyvinyl alcohol commonly used in the art, and described is poly-
The average degree of polymerization of vinyl alcohol is preferably 500～2500.
Wherein, the mass percent concentration of described polyvinyl alcohol water solution is preferably 10～15%.
Wherein, described polyvinyl alcohol water solution is preferably with the mass ratio of described metal dust
(1～3): 100.
Wherein, described metal dust is preferably tungsten 0～97%, molybdenum 0～97%, nickel 0～20%, copper
0～50% and ferrum 0～20%, but be asynchronously 0, percentage ratio is relative to described metal dust gross mass
Mass percent.Described metal dust is more preferably tungsten 90%, nickel 7% and the mixture of ferrum 3% composition,
Or the mixture of tungsten 97%, nickel 2%, ferrum 1% composition, or the mixture that tungsten 90% and copper 10% form,
Or the mixture that tungsten 80% and copper 20% form, or tungsten 93%, nickel 5% and the mixture of copper 2% composition,
Or tungsten 90%, nickel 7% and the mixture of copper 3% composition, or the mixture that molybdenum 85% and copper 15% form,
Or the mixture that molybdenum 80% and copper 20% form, or the mixture that molybdenum 50% and copper 50% form, or tungsten
93%, nickel 5% and the mixture of ferrum 2% composition.
Wherein, the method for described molding can be various powder metallurgy forming sides commonly used in the art
Method, preferably first carries out molding compressing, injection moulding or powder rolling, then is sintered.
The described specific mo(u)lding pressure molding compressing, injection moulding or powder rolling is preferably
0.5～1.0T/cm2(i.e. 0.5～1.0 ton/square centimeter), the temperature of described sintering is preferably
1300～1600 DEG C, described sintering is preferably in ammonia dissolving atmosphere, hydrogen atmosphere or (1.0～5.0) × 10-2Pa
It is sintered under vacuum atmosphere.
After pva powder is mixed by the present invention with water, being heated to 50～100 DEG C, stirring, it is poly-i.e. to obtain
Vinyl alcohol aqueous solution, at room temperature (10～30 DEG C) join in metal dust, stir, molding,
?.After the metal powder metallurgy molding of the present invention, the density of product is 9.45～18.4g/cm3Between.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can combination in any, i.e. get Ben Fa
Bright each preferred embodiments.
Agents useful for same of the present invention and raw material are the most commercially.
The most progressive effect of the present invention is: polyvinyl alcohol (PVA) aqueous solution of the present invention is difficult to wave
Send out, nonpoisonous and tasteless, pollution-free, use polyvinyl alcohol water solution as the adhesive in metal powder metallurgy
The problem that can effectively reduce the product quality inhomogeneities that volatile type adhesive causes, simultaneously follow-up
Sintering process is directly sloughed with stove and new degumming equipment and Degumming Procedures need not be increased, both protected ring
Border, decrease pollution, reduce again cost, the stability of product quality is increased guarantee simultaneously.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore limit the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to often
Rule method and condition, or select according to catalogue.
Embodiment 1
(1) pure water 1000g is weighed with electronic scale, and with the pva powder of electronic scale weighing 60g
(average degree of polymerization n is 1600～1800), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 50 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 0.5% and is mixed with tungsten (weight
Percentage ratio: 90%), nickel (percentage by weight: 7%), the mixed powder of ferrum (percentage by weight: 3%)
In end, uniform stirring.
(4) mixed-powder carrying out on powder rolls continuous rolling molding, unit width rolling pressure is
0.8T/cm2, under ammonia dissolving atmosphere, carry out 1500 DEG C of high temperature sinterings subsequently, 90WNiFe can be processed into
High specific gravity alloy material, the homogenous material properties obtained, test in different parts sampling, density
Up to 17.0 ± 0.15g/cm3, microhardness HRV (also referred to as Vickers hardness) is 285 ± 10, and carbon contains
Amount is less than 0.05wt%.
Embodiment 2
(1) pure water 1000g is weighed with electronic scale, and with the polyvinyl alcohol powder of electronic scale weighing 200g
End (average degree of polymerization n is 2400～2500), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 100 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 0.5% and is mixed with tungsten (weight
Percentage ratio: 97%), nickel (percentage by weight: 2%), the mixed powder of ferrum (percentage by weight: 1%)
In end, and stir.
(4) carry out molding compressing by mixed-powder, specific mo(u)lding pressure is 0.9T/cm2, then
1.5 × 10-2Carry out 1530 DEG C of high temperature sinterings under Pa vacuum atmosphere, can be prepared by 97WNiFe high specific gravity
Alloy part, the homogenous material properties obtained, to test in different parts sampling, density is up to 18.3
±0.15g/cm3, hardness HRV is 305 ± 10, and carbon content is less than 0.05wt%.
Embodiment 3
(1) pure water 1000g is weighed with electronic scale, and with the polyvinyl alcohol powder of electronic scale weighing 200g
End (average degree of polymerization n is 2000～2200), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 80 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 1.0% and is mixed with tungsten (weight
Percentage ratio: 90%), in the mixed-powder of copper (percentage by weight: 10%), uniform stirring.
(4) mixed-powder uses injection moulding method to be shaped, and briquetting pressure is 0.6T/cm2, so
After carry out 1480 DEG C of high temperature sinterings in a hydrogen atmosphere, can be prepared by 90WCu alloy material, obtained
Homogenous material properties, different parts sampling test, density is 17.1 ± 0.15g/cm3, firmly
Degree HRV is 260 ± 10, and carbon content is less than 0.05wt%.
Embodiment 4
(1) pure water 1000g is weighed with electronic scale, and with the polyvinyl alcohol powder of electronic scale weighing 150g
End (average degree of polymerization n is 1800～2000), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 100 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 5.0% and is mixed with tungsten (weight
Percentage ratio: 80%), in the mixed-powder of copper (percentage by weight: 20%), uniform stirring.
(4) mixed-powder carries out continuous rolling molding on powder rolls, unit width rolling pressure is
0.9T/cm2, carry out 1450 DEG C of high temperature sinterings the most in a hydrogen atmosphere, can be prepared by 80WCu alloy
Material, the homogenous material properties obtained, to test in different parts sampling, density is 15.4 ± 0.16
g/cm3, hardness HRV is 240 ± 9, and carbon content is less than 0.05wt%.
Embodiment 5
(1) pure water 1000g is weighed with electronic scale, and with the polyvinyl alcohol powder of electronic scale weighing 200g
End (average degree of polymerization n is 2400～2500), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 100 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 3.0% and is mixed with tungsten (weight
Percentage ratio: 93%), nickel (percentage by weight: 5%), the mixed powder of copper (percentage by weight: 2%)
In end, and stir.
(4) mixed-powder carries out molding compressing, and specific mo(u)lding pressure is 1.0T/cm2, then exist
Carry out 1500 DEG C of high temperature sinterings under ammonia dissolving atmosphere, can be prepared by 93WNiCu alloy material, obtained
Homogenous material properties, different parts sampling test, density is 17.6 ± 0.14g/cm3, firmly
Degree HRV is 290 ± 11, and carbon content is less than 0.05wt%.
Embodiment 6
(1) pure water 1000g is weighed with electronic scale, and with the pva powder of electronic scale weighing 60g
(average degree of polymerization n is 1800～2000), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 95 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 4.0% and is mixed with tungsten (weight
Percentage ratio: 90%), nickel (percentage by weight: 7%), the mixed powder of copper (percentage by weight: 3%)
In end, and stir.
(4) mixed-powder uses injection moulding to be shaped, and briquetting pressure is 0.7T/cm2, then exist
5.0×10-2Carry out 1450 DEG C of high temperature sinterings under Pa atmosphere, can be prepared by 90WNiCu alloy material, institute
The homogenous material properties obtained, tests in different parts sampling, and density is 17.1 ± 0.15g/cm3,
Hardness HRV is 280 ± 10, and carbon content is less than 0.05wt%.
Embodiment 7
(1) pure water 1000g is weighed with electronic scale, and with the polyvinyl alcohol powder of electronic scale weighing 150g
End (average degree of polymerization n is 1600～1800), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 90 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 5.0% and is mixed with molybdenum (weight
Percentage ratio: 85%), in the mixed-powder of copper (percentage by weight: 15%), and stir.
(4) mixed-powder carries out molding compressing, and specific mo(u)lding pressure is 1.0T/cm2, then exist
Carry out 1400 DEG C of high temperature sinterings under hydrogen atmosphere, can be prepared by 85MoCu alloy material, obtained
Homogenous material properties, tests in different parts sampling, and density is 9.9 ± 0.12g/cm3, hardness HRV
Being 230 ± 8, carbon content is less than 0.05wt%.
Embodiment 8
(1) pure water 1000g is weighed with electronic scale, and with the polyvinyl alcohol powder of electronic scale weighing 200g
End (average degree of polymerization n is 2200～2400), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 50 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 0.5% and is mixed with molybdenum (weight
Percentage ratio: 80%), in the mixed-powder of copper (percentage by weight: 20%), and stir.
(4) mixed-powder uses injection moulding to be shaped, and briquetting pressure is 0.6T/cm2, then exist
Carry out 1400 DEG C of high temperature sinterings under ammonia dissolving atmosphere, can be prepared by 80MoCu alloy material, obtained
Homogenous material properties, different parts sampling test, density is 9.85 ± 0.11g/cm3, hardness
HRV is 210 ± 9, and carbon content is less than 0.05wt%.
Embodiment 9
(1) pure water 1000g is weighed with electronic scale, and with the polyvinyl alcohol powder of electronic scale weighing 100g
End (average degree of polymerization n is 2400～2500), adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 70 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 5% and is mixed with molybdenum (weight hundred
Proportion by subtraction: 50%), in the mixed-powder of copper (percentage by weight: 50%), and stir.
(4) mixed-powder carries out continuous rolling molding on powder rolls, and unit width rolling pressure is
0.8T/cm2, under ammonia dissolving atmosphere, carry out 1300 DEG C of high temperature sinterings subsequently, can be prepared by 50MoCu and close
Gold copper-base alloy, the homogenous material properties obtained, to test in different parts sampling, density is
9.45±0.13g/cm3, hardness HRV is 145 ± 8, and carbon content is less than 0.05wt%.
Embodiment 10
(1) pure water 1000g is weighed with electronic scale, and with electronic scale weighing 100g average degree of polymerization n
It is the pva powder of 500～700, adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 80 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 3% and is mixed with molybdenum (weight hundred
Proportion by subtraction: 85%), in the mixed-powder of copper (percentage by weight: 15%), and stir.
(4) mixed-powder carries out continuous rolling molding on powder rolls, and unit width rolling pressure is
0.8T/cm2, carry out 1350 DEG C of high temperature sinterings the most in a hydrogen atmosphere, prepare 85MoCu alloy material,
The homogenous material properties obtained, tests in different parts sampling, and density is 9.9 ± 0.11g/cm3,
Hardness HRV is 230 ± 10, and carbon content is less than 0.05wt%.
Embodiment 11
(1) pure water 1000g is weighed with electronic scale, and with electronic scale weighing 60g average degree of polymerization n
It is the pva powder of 1100～1300, adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 70 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 1.5% and is mixed with tungsten (weight
Percentage ratio: 93%), nickel (percentage by weight: 5%), the mixed powder of ferrum (percentage by weight: 2%)
In end, uniform stirring.
(4) mixed-powder carrying out on powder rolls continuous rolling molding, unit width rolling pressure is
0.8T/cm2, under ammonia dissolving atmosphere, carry out 1500 DEG C of high temperature sinterings subsequently, be processed into 93WNiFe high
Gravity alloy material, the homogenous material properties obtained, to test in different parts sampling, density is
17.5±0.15g/cm3, hardness HRV is 290 ± 9, and carbon content is less than 0.05wt%.
Comparative example 1
(1) pure water 1000g is weighed with electronic scale, and with electronic scale weighing 40g average degree of polymerization n
It is the pva powder of 1100～1300, adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 70 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 0.5% and is mixed with tungsten (weight
Percentage ratio: 93%), nickel (percentage by weight: 5%), the mixed powder of ferrum (percentage by weight: 2%)
In end, uniform stirring.
(4) mixed-powder carrying out on powder rolls continuous rolling molding, unit width rolling pressure is
0.8T/cm2, under ammonia dissolving atmosphere, carry out 1500 DEG C of high temperature sinterings subsequently, be processed into 93WNiFe high
Gravity alloy material, the material property obtained is uniform not, tests in different parts sampling, close
Degree is 17.5 ± 0.3g/cm3, hardness HRV is 290 ± 15, and carbon content is less than 0.05wt%.
Comparative example 2
(1) pure water 1000g is weighed with electronic scale, and with electronic scale weighing 300g average degree of polymerization n
It is the pva powder of 1100～1300, adds in the container filling pure water.
(2) use electromagnetic oven that the beaker being filled with water is heated to 70 DEG C, and continuously stirred, until
It is made into homogeneous solution.
(3), under room temperature, this poly-vinyl alcohol solution is added according to the weight ratio of 5.5% and is mixed with tungsten (weight
Percentage ratio: 93%), nickel (percentage by weight: 5%), the mixed powder of ferrum (percentage by weight: 2%)
In end, uniform stirring.
(4) mixed-powder carrying out on powder rolls continuous rolling molding, unit width rolling pressure is
0.8T/cm2, under ammonia dissolving atmosphere, carry out 1500 DEG C of high temperature sinterings subsequently, be processed into 93WNiFe high
Gravity alloy material, the material property obtained is uniform not, tests in different parts sampling, close
Degree is 17.5 ± 0.5g/cm3, hardness HRV is 290 ± 35, and carbon content is 0.08wt%.
Claims (10)
1. the polyvinyl alcohol water solution application in metal powder metallurgy molding, it is characterised in that
The mass percent concentration of described polyvinyl alcohol water solution is 5～20%, and described metal dust includes
One or more in tungsten, molybdenum, nickel, copper and ferrum；Described polyvinyl alcohol water solution and described metal
The mass ratio of powder is (0.5～5): 100.
Apply the most as claimed in claim 1, it is characterised in that the average of described polyvinyl alcohol gathers
Right is 500～2500.
Apply the most as claimed in claim 1, it is characterised in that described polyvinyl alcohol water solution
Mass percent concentration is 10～15%.
Apply the most as claimed in claim 1, it is characterised in that described polyvinyl alcohol water solution with
The mass ratio of described metal dust is (1～3): 100.
Apply the most as claimed in claim 1, it is characterised in that described metal dust be tungsten 0～97%,
Molybdenum 0～97%, nickel 0～20%, copper 0～50% and ferrum 0～20%, but be asynchronously 0, percentage ratio is relative
Mass percent in described metal dust gross mass.
Apply the most as claimed in claim 5, it is characterised in that described metal dust be tungsten 90%,
Nickel 7% and the mixture of ferrum 3% composition, or the mixture of tungsten 97%, nickel 2%, ferrum 1% composition, or
Tungsten 90% and the mixture of copper 10% composition, or the mixture that tungsten 80% and copper 20% form, or tungsten 93%,
Nickel 5% and the mixture of copper 2% composition, or tungsten 90%, nickel 7% and the mixture of copper 3% composition, or
Molybdenum 85% and the mixture of copper 15% composition, or the mixture that molybdenum 80% and copper 20% form, or molybdenum 50%
The mixture formed with copper 50%, or tungsten 93%, nickel 5% and the mixture of ferrum 2% composition.
Apply the most as claimed in claim 1, it is characterised in that described being shaped to first molds
Compressing, injection moulding or powder rolling, then be sintered.
Apply the most as claimed in claim 7, it is characterised in that described mold pressing is compressing, note
The specific mo(u)lding pressure penetrating molding or powder rolling is 0.5～1.0T/cm2。
Apply the most as claimed in claim 7, it is characterised in that the temperature of described sintering is
1300～1600 DEG C.
Apply the most as claimed in claim 7, it is characterised in that described be sintered in ammonia dissolving atmosphere,
Hydrogen atmosphere or (1.0～5.0) × 10-2It is sintered under Pa vacuum atmosphere.
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| CN108149101A (en) * | 2017-08-13 | 2018-06-12 | 广东省材料与加工研究所 | A kind of manufacturing process of high-density large-area tungsten-copper alloy life slab |
| CN114247888B (en) * | 2021-12-08 | 2024-04-09 | 蓝山县金山川粉末冶金有限公司 | Method for manufacturing transmission gear through powder metallurgy |
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| JPH02141502A (en) * | 1988-11-18 | 1990-05-30 | Komatsu Ltd | Manufacture of metal sintered product |
| CN101058862A (en) * | 2007-05-26 | 2007-10-24 | 潍坊富源增压器有限公司 | Booster turbine and method of manufacturing the same |
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