A kind of processing method of the siller tin oxide electric contact material containing additive
Technical field
The processing method that the present invention relates to a kind of siller tin oxide electric contact material containing additive, belongs to metal
Based composites field.
Background technology
In recent years, siller tin oxide contact extensively should as the optimal replacer of poisonous silver cadmium oxide contact
It is used in various low-voltage electrical apparatus.Sliver oxidized tin contactor materials has excellent wearability, resistance fusion welding and resistance to
Arc erosion, but there is the shortcomings such as contact resistance is big, temperature rise is high in it, has had a strong impact on the electrical resistance of electrical equipment
Energy.
Discovery is studied, one or more oxidations being added with in bismuth oxide, copper oxide and Indium sesquioxide. through forefathers
The siller tin oxide electric contact material of thing not only has good wearability, resistance fusion welding and resistance to arc erosion,
Improve the electric property of electrical equipment well.As a rule, the system of the siller tin oxide electric contact containing additive
Standby technique mainly has three kinds: powder mixing method, internal oxidation and Chemical coating method.Powder mixing method is to be mixed by machinery
Conjunction mode mixes argentum powder, putty powder and additive powder body, then mixed powder is shaped,
A series of processing such as sintering, extruding, finally obtain the siller tin oxide electric contact containing additive.This method
Preparation technology is simple, the process-cycle is short, but the problem that additive is assembled easily occurs.Internal oxidation refers to
Silver-colored ashbury metal containing addition element is prepared the silver tin oxide material containing additive by oxidation, then carries out
Molding, sinter, a series of processing such as extruding, finally obtain the siller tin oxide electric contact containing additive.Should
The shortcoming of the method for kind is easily to occur lean oxide region in material structure, affects the electrical property of material.Change
Learn cladding process to refer to prepare the siller tin oxide electric contact material containing additive by chemical clading process.Should
The deficiency of the method for kind is the reduction needing to use the noxious substance to human body and bad environmental as course of reaction
Agent, is unfavorable for the sustainable development of society.
Through prior art is retrieved, the patent of invention of Publication No. CN102389981A, disclose one
Plant the method that continuous uniform prepares silver tin oxide material.First the method is by ultrasound wave Homogenization Treatments
After stannum oxide slurry mix with silver nitrate solution, then by two together with ascorbic acid solution
Platform pump is got in reactor and is reacted, and obtains elemental silver and is compounded in equably on the surface of stannum oxide.Should
Method is not directed to the interpolation of metallic additions, is dispersed in matrix to additive of sening as an envoy to
Method.
The patent of invention of Publication No. CN1234591A, discloses a kind of synthesis method for preparing silver-tin dioxide
Contact material.Silver, silver oxide, stannum, stannum oxide, stannous sulfate and addition element are passed through by this invention
Batch mixing aftershaping, is then pressed into the pressed compact after molding silver liquation and is synthesized, more laggard through ingot casting
Siller tin oxide electric contact is processed in row extruding, wire drawing etc..But the method existence easily occurs that additive is assembled
Deficiency.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is simple, additive is in matrix material point
Cloth contains the processing method of the siller tin oxide electric contact material of additive, silver oxygen obtained by this method uniformly
Change stannum electrical contact metallographic structure is uniform, have excellent processing characteristics.
The processing method of the siller tin oxide electric contact material containing additive of the present invention, including following step
Rapid:
1) metallic tin needed for calculating according to the material mixture ratio of the siller tin oxide electric contact of required preparation, gold
Belonging to additive and the consumption of silver, required silver is divided into two parts, a part is with the form of argent and gold
Genus stannum and metallic additions are smelted into uniform alloy molten solution, then through mist in being together placed in mid-frequency melting furnace
Change and make silver ashbury metal powder;Another part weighs standby with the form of silver nitrate, and according to the use of silver nitrate
Amount calculates the consumption of the sodium hydroxide needed for silver nitrate and sodium hydroxide reaction generation silver oxide, weighs standby;
Take silver nitrate water dissolution and be made into the silver nitrate solution of 20~40wt%, by molten to silver ashbury metal powder and silver nitrate
Liquid is placed in reactor, stirs, and obtains silver nitrate and the suspension of silver ashbury metal powder;Described gold
Belonging to additive is one or more the combination in bismuth, copper and indium;
2) take sodium hydroxide water dissolution and be made into the sodium hydroxide solution of 10~30wt%, join step 1)
Stirring reaction in the suspension of gained, has precipitation to generate, filters, and obtains silver oxide and silver the answering of ashbury metal
Close powder;
3) by the silver oxide of gained and silver ashbury metal composite powder be washed to neutrality, be dried, pulverize rearmounted
Aoxidize in oxygen-containing atmosphere, then pulverize, obtain the siller tin oxide composite powder containing additive;
4) by the siller tin oxide composite powder isostatic pressing containing additive of gained, it is placed in oxygenous the most again
Atmosphere sinters, obtains the siller tin oxide billet containing additive;
5) gained siller tin oxide billet through hot extrusion be processed into band or wire rod, after through Rolling compund or draw
Pull out, more stamped processing or rivet driver are processed, and i.e. obtain lamellar or the rivet type siller tin oxide containing additive
Electrical contact material.
Required silver is divided into two parts by the present invention, and a part is with the form of argent and metallic tin and metal
Additive is smelted into uniform alloy molten solution in being together placed in mid-frequency melting furnace, then make containing adding through atomization
Add the silver-colored ashbury metal powder of thing;Another part silver closes with the silver-colored stannum containing additive prepared with the form of silver nitrate
React with sodium hydroxide again after bronze mixing and obtain silver oxide and the composite powder of silver ashbury metal, due to silver stannum
Density (about 8.5~the 9.6g/cm of alloyed powder3) and the silver oxide (7.143g/cm of reaction generation3) close
Degree relatively, thus can make silver oxide and silver ashbury metal powder mix evenly so that silver oxide
Grain is more uniformly distributed in silver ashbury metal powder, so that gained contact material has uniform metallographic
Tissue;On the other hand, the silver oxygen that produced by silver oxide decomposes in oxidizing process of ashbury metal powder with
Silver ashbury metal generation reaction in-situ, decreases the tin element diffusion to granule top layer, accelerates silver ashbury metal
The oxidation of powder;Simultaneously as silver tin alloy particles plays in silver nitrate with the course of reaction of sodium hydroxide
The effect of reaction intermediary so that a part of silver oxide that reaction generates can cover at silver tin alloy particles
Surface, improve the adhesion between the second phase (i.e. stannum oxide phase), it is to avoid present in prior art
Directly contact between brittlement phase (i.e. stannum oxide phase), so that contact material has more preferable processability
Energy.
The step 1 of said method) in, the described siller tin oxide electric contact material containing additive needing preparation
In, stannum oxide content is 8~18wt%, and the content of metallic additions is 0.1~2.5wt%, and surplus is silver;
The preferred stannum oxide content that is chosen as is 10~12wt%, and the content of metallic additions is 0.5~1wt%,
Surplus is silver.In this step, preferably silver nitrate is configured to the silver nitrate solution of 30~40wt%, more
Preferably it is configured to the silver nitrate solution of 30~35wt%, so can make the metallographic of gained electrical contact material
Tissue is more uniformly distributed.In this step, the consumption of sodium hydroxide is usually the 4/17~5/17 of silver nitrate consumption,
More preferably 4.4/17.When two or more combination during metallic additions is bismuth, copper and indium, full
The foot total addition of metallic additions account for siller tin oxide electric contact material gross mass containing additive 0.1~
Time in the range of 2.5wt%, the proportioning between them can be any proportioning.
The step 1 of said method) in, described together put with metallic tin and metallic additions with argent form
In mid-frequency melting furnace, the argent of melting accounts for the ratio of the total consumption of silver and is usually 10~80wt%.
The step 2 of said method) in, the addition speed of described sodium hydroxide solution be preferably 0.1~
1L/min;The concentration of described sodium hydroxide solution is preferably 15~25wt%, and gained electricity so can be made to touch
The metallographic structure of head material is more uniformly distributed.In this step, stirring reaction is generally carried out under normal temperature condition,
The time of stirring reaction is usually 0.3~1h.
The step 3 of said method) in, the operation being dried and pulverizing is same as the prior art, in the application,
Preferably it is dried under the conditions of 100~150 DEG C until the composite powder of silver oxide and silver ashbury metal is dried i.e.
Can, it usually needs the time of 12~18h;Be typically dried silver oxide and silver ashbury metal is compound
Powder crosses 100~200 eye mesh screens after pulverizing, and extracting screen underflow enters next process.Described oxidation is preferred
Be oxygen pressure be 0.1~1.0MPa, temperature be 400~800 DEG C under the conditions of carry out, the time of oxidation be 6~
12h。
The step 4 of said method) in, described isostatic pressing and sintering operation and existing routine operation phase
With, specifically, the briquetting pressure of isostatic pressing is usually 100~150MPa;It is typically isostatic pressed
Pressed compact after molding is placed in oxygen-containing atmosphere under 880~920 DEG C of temperature conditionss sintering 4~8h, to obtain
Siller tin oxide billet containing additive.
The step 5 of said method) in, described hot extrusion etc. operates all identical with existing routine operation, tool
Body ground, the temperature of hot extrusion is usually 750~900 DEG C, and extrusion ratio is 10~200.When containing additive
Siller tin oxide billet hot extrusion when being processed into band, gained band through repeatedly Rolling compund, be annealed to institute
Need after size through punch press punching press, obtain the siller tin oxide electric contact material containing additive of lamellar.When containing
When wire rod is processed in the siller tin oxide billet hot extrusion of additive, gained wire rod arrives through repeatedly drawing and annealing
Process through rivet driver after required size, obtain the siller tin oxide electric contact material containing additive of rivet type.
Compared with prior art, present invention is characterized in that
1, required silver is divided into two parts by the present invention, and a part is with the form of argent and metallic tin and gold
Belong in additive is together placed in mid-frequency melting furnace and be smelted into uniform alloy molten solution, then make through atomization and contain
The silver-colored ashbury metal powder of additive;Another part silver is with the form of silver nitrate and the Yin Xi containing additive prepared
React with sodium hydroxide again after alloyed powder mixing and obtain silver oxide and the composite powder of silver ashbury metal, due to silver
Density (about 8.5~the 10.5g/cm of ashbury metal powder3) and the silver oxide (7.143g/cm of reaction generation3)
Density relatively, thus can make silver oxide and silver ashbury metal powder mix evenly so that silver oxide
Granule is more uniformly distributed in silver ashbury metal powder, so that gained contact material has uniform gold
Phase constitution;On the other hand, the oxygen that silver ashbury metal powder is produced by silver oxide decomposes in oxidizing process
With silver ashbury metal generation reaction in-situ, decrease the tin element diffusion to granule top layer, accelerate Yin Xihe
The oxidation of bronze;Simultaneously as silver tin alloy particles rises in silver nitrate with the course of reaction of sodium hydroxide
Effect to reaction intermediary so that a part of silver oxide that reaction generates can cover at silver tin alloy particles
Surface, improve the adhesion between the second phase (i.e. stannum oxide phase), it is to avoid prior art exists
Brittlement phase (i.e. stannum oxide phase) between directly contact so that contact material has preferably processing
Performance.
2, the method for the invention technique is simple, little to human body and environmental pollution, is suitable for industrialized production.
Accompanying drawing explanation
Fig. 1 is the metallographic structure figure (200 ×) of the contact material that the embodiment of the present invention 1 prepares;
Fig. 2 is the metallographic structure figure (200 ×) of the contact material that the embodiment of the present invention 2 prepares;
Fig. 3 is the metallographic structure figure (200 ×) of the contact material that the embodiment of the present invention 3 prepares;
Fig. 4 is the metallographic structure figure (200 ×) of the contact material that the embodiment of the present invention 4 prepares.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, to be more fully understood that the present invention's
Content, but the present invention is not limited to following example.
Embodiment 1
1) it is first according to prepare 10kg Ag-SnO2(11)-In2O3(1.5) material mixture ratio calculate required indium metal,
Silver, the consumption of stannum, weigh pure indium block 0.012kg, block tin 0.866kg standby, the total amount of silver is divided
Becoming two parts, a portion is the fine silver block of 4.896kg, and another part is the silver nitrate of 6.066kg,
Weigh standby, further according to consumption weighing sodium hydroxide 1.57kg of silver nitrate, standby;
2) uniform conjunction it is smelted in the pure indium block, block tin and the fine silver block that weigh being placed in mid-frequency melting furnace
Gold liquation, is then atomized through hydraulic atomized equipment, is dried by the powder slurries obtained, crosses 200
Mesh sieve, obtains silver tin-indium alloy powder;
3) take silver nitrate water dissolution and be made into the silver nitrate solution of 40wt%, by the silver-colored tin-indium alloy powder of gained
End and silver nitrate solution are placed in reactor, stir, and obtain the outstanding of silver nitrate and silver tin-indium alloy powder
Supernatant liquid;
4) take sodium hydroxide water and be made into the sodium hydroxide solution of 30wt%, under stirring condition, to above-mentioned institute
Obtain the sodium hydroxide solution (drop rate is 0.3L/min) adding 30wt% in suspension, react 0.5h,
Silver oxide and the composite powder of silver tin-indium alloy is obtained after filtration;
5) during the silver oxide above-mentioned reaction obtained and silver tin-indium alloy composite powder deionized water clean extremely
Property, dry 15h with 120 DEG C of temperature the most in an oven, then by the silver oxide dried and silver tin-indium alloy
Composite powder is placed in bipyramid blender broken (rotating speed 25r/min, time 1h);Gained powder is placed in oxygen
Atmospheric pressure be 0.5MPa oxygen atmosphere under the conditions of 750 DEG C aoxidize 10h, cross 200 mesh sieves, obtain
Silver-tin oxide or indium oxide composite powder;
6) gained composite powder molding on isostatic pressing machine (briquetting pressure is 150MPa), and by the pressure after molding
Base is placed in air with 880 DEG C of temperature sintering 4h, obtains silver-tin oxide or indium oxide billet;
7) wire rod is processed in the hot extrusion of gained silver-tin oxide or indium oxide billet, and extrusion temperature is 850 DEG C,
Mold preheating temperature is 150 DEG C, and extrusion ratio is 190;Gained wire rod again through repeatedly drawing and annealing to required
It is processed into the silver-tin oxide or indium oxide of rivet type with rivet driver after the size wanted
(Ag-SnO2(11)-In2O3(1.5)) electrical contact.
Gained contact material is carried out metallographic structure analysis, as it is shown in figure 1, present techniques as seen from the figure
The metallographic structure of contact product prepared by scheme is uniform, and tiny stannum oxide and indium oxide particles divide equably
Cloth is in silver matrix.
Embodiment 2
1) it is first according to prepare 10kg Ag-SnO2(11)-Bi2O3(1.5)-CuO (1.0) material mixture ratio calculates institute
Need the consumption of bismuth metal, copper, silver, stannum, weigh pure bismuth block 0.013kg, fine copper block 0.008kg, pure tin
Block 0.866kg is standby, and the total amount of silver is divided into two parts, and a portion is the fine silver block of 4.887kg,
Another part is the silver nitrate of 5.923kg, weighs standby, and the consumption further according to silver nitrate weighs hydroxide
Sodium 1.533kg, standby;
2) it is smelted in the bismuth block weighed, fine copper block, block tin and fine silver block being placed in mid-frequency melting furnace all
Even alloy molten solution, is then atomized through hydraulic atomized equipment, is dried by the powder slurries obtained,
Cross 200 mesh sieves, obtain silver stannum bismuth copper alloy powder;
3) take silver nitrate water dissolution and be made into the silver nitrate solution of 30wt%, by the silver-colored stannum bismuth copper alloy of gained
Powder and silver nitrate solution are placed in reactor, stir, and obtain silver nitrate and Yin Xi bismuth copper alloy powder
Suspension;
4) take sodium hydroxide water and be made into the sodium hydroxide solution of 10wt%, under stirring condition, to above-mentioned institute
Obtain the sodium hydroxide solution (drop rate is 1L/min) adding 10wt% in suspension, react 0.8h, mistake
Silver oxide and the composite powder of Yin Xi bismuth copper is obtained after filter;
5) silver oxide above-mentioned reaction obtained and Yin Xi bismuth copper alloy composite powder deionized water clean extremely
Neutrality, dries 18h with 100 DEG C of temperature, the most in an oven then by the silver oxide dried and Yin Xi bismuth copper
Alloy composite powder is placed in bipyramid blender broken (rotating speed 25r/min, time 1h);Gained powder is put
In the oxygen atmosphere that oxygen pressure is 1.0MPa, under the conditions of 720 DEG C, aoxidize 6h, cross 200 mesh sieves,
To siller tin oxide bismuth oxide copper oxide composite powder;
6) gained composite powder molding on isostatic pressing machine (briquetting pressure is 120MPa), and by the pressure after molding
Base is placed in air with 900 DEG C of temperature sintering 6h, obtains siller tin oxide bismuth oxide copper oxide billet;
7) band is processed in the billet hot extrusion of gained siller tin oxide bismuth oxide copper oxide, and extrusion temperature is 850
DEG C, mold preheating temperature is 150 DEG C, and extrusion ratio is 160;Again by band through repeatedly Rolling compund, move back
Fire is to the siller tin oxide bismuth oxide copper oxide being processed into lamellar after required size with punch press
(Ag-SnO2(11)-Bi2O3(1.5)-CuO (1.0)) electrical contact.
Gained contact material is carried out metallographic structure analysis, as in figure 2 it is shown, present techniques as seen from the figure
The metallographic structure of contact product prepared by scheme is uniform, tiny stannum oxide, bismuth oxide and copper oxide particle
It is evenly distributed in silver matrix.
Embodiment 3
1) it is first according to prepare 10kg Ag-SnO2(18)-CuO (0.1) material mixture ratio calculate required metallic copper,
Silver, the consumption of stannum, weigh fine copper block 0.008kg, block tin 1.417kg standby, the total amount of silver is divided
Becoming two parts, a portion is the fine silver block of 5.66kg, and another part is the silver nitrate of 3.982kg,
Weigh standby, further according to consumption weighing sodium hydroxide 1.031kg of silver nitrate, standby;
2) uniform conjunction it is smelted in the fine copper block weighed, block tin and fine silver block being placed in mid-frequency melting furnace
Gold liquation, is then atomized through hydraulic atomized equipment, is dried by the powder slurries obtained, crosses 200
Mesh sieve, obtains silver gun-metal powder;
3) take silver nitrate water dissolution and be made into the silver nitrate solution of 25wt%, by the silver-colored gun-metal powder of gained
End and silver nitrate solution are placed in reactor, stir, and obtain the outstanding of silver nitrate and silver gun-metal powder
Supernatant liquid;
4) take sodium hydroxide water and be made into the sodium hydroxide solution of 20wt%, under stirring condition, to above-mentioned institute
Obtain the sodium hydroxide solution (drop rate is 1L/min) adding 20wt% in suspension, react 0.5h, mistake
Silver oxide and the composite powder of Yin Xi copper is obtained after filter;
5) during the silver oxide above-mentioned reaction obtained and silver gun-metal composite powder deionized water clean extremely
Property, dry 18h with 100 DEG C of temperature the most in an oven, then by the silver oxide dried and silver gun-metal
Composite powder is placed in bipyramid blender broken (rotating speed 25r/min, time 1h);Gained powder is placed in oxygen
Atmospheric pressure be 0.8MPa oxygen atmosphere under the conditions of 680 DEG C aoxidize 12h, cross 200 mesh sieves, obtain
Siller tin oxide copper oxide composite powder;
6) gained composite powder molding on isostatic pressing machine (briquetting pressure is 150MPa), and by the pressure after molding
Base is placed in air with 920 DEG C of temperature sintering 6h, obtains siller tin oxide copper oxide billet;
7) band is processed in the billet hot extrusion of gained siller tin oxide copper oxide, and extrusion temperature is 850 DEG C,
Mold preheating temperature is 150 DEG C, and extrusion ratio is 150;Again by band through repeatedly Rolling compund, be annealed to
It is processed into the siller tin oxide copper oxide of lamellar with punch press after required size
(Ag-SnO2(18)-CuO (0.1)) electrical contact.
Gained contact material is carried out metallographic structure analysis, as it is shown on figure 3, present techniques as seen from the figure
The metallographic structure of contact product prepared by scheme is uniform, and tiny stannum oxide and copper oxide particle divide equably
Cloth is in silver matrix.
Embodiment 4
1) it is first according to prepare 10kg Ag-SnO2(12)-In2O3(0.5)-Bi2O3(0.5)-CuO (0.5) material
Proportioning calculates required indium metal, bismuth metal, metallic copper, silver, the consumption of stannum, weigh fine copper block 0.04kg,
Pure bismuth block 0.045kg, pure indium block 0.041kg, block tin 0.945kg are standby, the total amount of silver are divided into
Two parts, a portion is the fine silver block of 5.228kg, and another part is the silver nitrate of 5.386kg,
Weigh standby, further according to consumption weighing sodium hydroxide 1.394kg of silver nitrate, standby;
2) the pure indium block weighed, pure bismuth block, fine copper block, block tin and fine silver block are placed in mid-frequency melting furnace
Inside it is smelted into uniform alloy molten solution, is then atomized through hydraulic atomized equipment, the powder that will obtain
Slurry is dried, and crosses 200 mesh sieves, obtains silver stannum indium bismuth copper alloy powder;
3) take silver nitrate water dissolution and be made into the silver nitrate solution of 30wt%, the silver-colored stannum indium bismuth copper of gained is closed
Bronze end and silver nitrate solution are placed in reactor, stir, and obtain silver nitrate and Yin Xi indium bismuth copper closes
The suspension of bronze;
4) take sodium hydroxide water and be made into the sodium hydroxide solution of 25wt%, under stirring condition, to above-mentioned institute
Obtain the sodium hydroxide solution (drop rate is 1L/min) adding 25wt% in suspension, react 0.5h, mistake
Silver oxide and the composite powder of Yin Xi indium bismuth copper is obtained after filter;
5) silver oxide and the Yin Xi indium bismuth copper alloy composite powder deionized water that above-mentioned reaction are obtained clean
To neutral, dry 15h with 120 DEG C of temperature the most in an oven, then by the silver oxide dried and Yin Xi indium
Bismuth copper alloy composite powder is placed in bipyramid blender broken (rotating speed 25r/min, time 1h);Gained powder
End is placed in the oxygen atmosphere that oxygen pressure is 0.1MPa and aoxidizes 8h under the conditions of 700 DEG C, crosses 200 mesh sieves,
Obtain silver-tin oxide or indium oxide bismuth oxide copper oxide composite powder;
6) gained composite powder molding on isostatic pressing machine (briquetting pressure is 150MPa), and by the pressure after molding
Base is placed in air with 920 DEG C of temperature sintering 6h, obtains silver-tin oxide or indium oxide bismuth oxide copper oxide billet;
7) band, hot extrusion temperature are processed in the billet hot extrusion of gained silver-tin oxide or indium oxide bismuth oxide copper oxide
Degree is 850 DEG C, and mold preheating temperature is 150 DEG C, and extrusion ratio is 150;Again by band through repeatedly rolling
Be combined, be annealed to required size after be processed into the silver-tin oxide or indium oxide bismuth oxide oxygen of lamellar with punch press
Change copper (Ag-SnO2(12)-In2O3(0.5)-Bi2O3(0.5)-CuO (0.5)) electrical contact.
Gained contact material is carried out metallographic structure analysis, as shown in Figure 4, present techniques as seen from the figure
The metallographic structure of contact product prepared by scheme is uniform, tiny stannum oxide, Indium sesquioxide., bismuth oxide and oxygen
Change copper granule to be evenly distributed in silver matrix.
The contact material that embodiment 1 prepares is carried out performance detection, and mixes powder-extruding legal system with existing routine
The contact product of siller tin oxide adding Indium sesquioxide. compare, result the most following Tables 1 and 2 institute
Show:
Table 1: embodiment 1 and existing routine mix wire product performance prepared by powder-squeezing and pressing method
Table 2 embodiment 1 and existing routine mix the electric life of rivet type contact prepared by powder-squeezing and pressing method
From Tables 1 and 2, the performance of sliver oxidized tin contactor materials prepared by technical scheme is excellent
Powder-squeezing and pressing method sliver oxidized tin contactor materials performance is mixed in existing routine.