CN101824619B - Preparation method of foam tin material - Google Patents
Preparation method of foam tin material Download PDFInfo
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- CN101824619B CN101824619B CN2010101895434A CN201010189543A CN101824619B CN 101824619 B CN101824619 B CN 101824619B CN 2010101895434 A CN2010101895434 A CN 2010101895434A CN 201010189543 A CN201010189543 A CN 201010189543A CN 101824619 B CN101824619 B CN 101824619B
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Abstract
The invention relates to a preparation method of foam tin material, which comprises the following steps that: polymeric sponge is sequentially coarsened, neutralized, presoaked, activated and peptized; then the peptized polymeric sponge is chemically tinned for 10 to 30min at 80 to 95DEG C in a solution with the pH value of 7 to 10, and finally electrolytically tinned to obtain the foam tin material; and the solution contains 5 to 10g/L of stannous chloride, 80 to 150g/L of the mixture of one or more of citric acid, potassium citrate, sodium citrate and citric acid ammonium salt, 5 to 20g/L of the mixture of one or more of EDTA, EDTA potassium salt, EDTA sodium and EDTA ammonium salt, 5 to 10g/L of nitrilotriacetic acid, 0.75 to 3.75g/L of titanium trichloride, and 5 to 30g/L of acetate. The preparation method of the foam tin material has simple process and is convenient to operate, and the prepared foam tin material has the advantages of a certain strength, light weight, large specific surface area, high through-hole rate, easy welding and the like.
Description
Technical field
The present invention relates to a kind of preparation method of foam tin material.
Background technology
Foam tin material can be widely used in fields such as automobile, chemical industry, electronics.The preparation method of conventional foam tin material; Normally polyurethane sponge is carried out electroless copper or chemical nickel plating after through alligatoring, sensitization, activation, dispergation; And then,, thereby form foam tin material at the electroplating surface layer of metal tin of foam copper or nickel foam through electric plating method.The foam tin that this method prepares; Its conductive layer is metallic copper or nickel, under some corrosive medium condition, after the metallic tin of foam tin surfaces is corroded; The metallic copper of bottom or nickel can be exposed in the corrosive medium environment, thereby can change the chemical property of foam tin material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of foam tin material.This preparing method's technology is simple, easy to operate; The foam tin material for preparing have certain intensity, in light weight, specific surface area is big, through-hole rate is high, be easy to the welding, key of the present invention is: do not adopt electroless copper or chemical nickel plating as electroconductive coating, directly adopt chemical tin plating process; The foam tin material purity that obtains is high; Impurity is few, the coating soft texture, and porosity is low.
For solving technical problem proposed by the invention, the technical scheme that the present invention adopts is:
A kind of preparation method of foam tin material; Its difference is: it may further comprise the steps: polyurethane sponge is carried out alligatoring, neutralization, preimpregnation, activation, dispergation successively; Then with the polyurethane sponge behind the dispergation in the pH value is 7～10 solution; Chemical plating stannum is 10～30 minutes under 80～95 ℃ of temperature, passes through eleetrotinplate at last, obtains foam tin material; Said solution comprises tin protochloride 5～10g/L; Mixture 80～the 150g/L of one or more of Hydrocerol A, Hydrocerol A sylvite, sodium citrate salt, Hydrocerol A ammonium salt; Mixture 5～the 20g/L of one or more of EDTA, EDTA sylvite, EDTA sodium salt, EDTA ammonium salt; Nitrilotriacetic acid(NTA) 5～10g/L, titanous chloride 2.25～3.75g/L, acetate 5～30g/L.
In the such scheme; Described alligatoring step is specially: polyurethane sponge was soaked in the strongly acidic solution etch 1～15 minute; Described strongly acidic solution is a kind of of following three kinds of mixed solutions: the mixed solution of being made up of sulfuric acid 100～500ml/L and SRM 935a 5～50g/L; The mixed solution of forming by chromic anhydride 10～100g/L and SRM 935a 5～50g/L, the mixed solution of forming by sulfuric acid 100～500ml/L, chromic anhydride 10～100g/L and SRM 935a 5～50g/L.
In the such scheme, described neutralization procedure is specially: the polyurethane sponge after the alligatoring was soaked in 50～100g/L sodium hydroxide solution 1～10 minute.Its role is to the acidic solution that the neutralization materials surface does not clean up, avoid hexavalent chromium to be brought in the preimpregnation groove, presoak is worked the mischief.
In the such scheme, described preimpregnation step is specially: the polyurethane sponge after will neutralizing, in presoak, soaked 1～30 minute, and described presoak is the mixed solution of tin protochloride 10～100g/L and hydrochloric acid 20～200ml/L.
In the such scheme; Described activation step is specially: the polyurethane sponge after the preimpregnation is soaked in carried out activation treatment in the activation solution 1～30 minute, described activation solution is the mixed solution of tin protochloride 20～100g/L, Palladous chloride 0.1～5g/L, hydrochloric acid 100～500ml/L, sodium stannate 5～10g/L.
In the such scheme, described dispergation step is specially: the polyurethane sponge after the activation is carried out dispergation handled 1～30 minute in 100～200ml/L hydrochloric acid soln.
In the such scheme; The concrete steps of described eleetrotinplate are: the polyurethane sponge behind chemical plating stannum is made cathode; Pure tin plate is made anode, and in the solution of the inferior tin 10～50g/L of sulfur acid, sulfuric acid 50～100ml/L, acid zinc-plated additive 10～50ml/L, cathode current density is 1～2A/dm
2, electroplated 60～150 minutes for 10～20 ℃, the zinc-plated additive of said acidity by one or both mixture, benzylideneacetone, TX10 of Hydrocerol A or Citrate trianion by mass ratio (5～10): 1: (5～10) mixed preparing forms.
In the such scheme, among the preparation method of described foam tin material,, the eleetrotinplate step carries out passivation after accomplishing: soaked for 5～30 seconds with 50～100g/L potassium bichromate solution, washing, drying.It can reduce the oxidation rate of tin in depositing process.
In the such scheme, adopt the secondary reverse-flow rinsing process to clean between described each step.It can clean up the impurity of each inter process.
In the such scheme, the thickness of coating of the foam tin material that the preparation method of said foam tin material prepares is 50～500 microns, and the aperture is 1～3 millimeter, and through-hole rate is 85～90%.
Beneficial effect of the present invention: (1) adopts the polyurethane sponge surface of chemical reduction method after handling through alligatoring, neutralization, preimpregnation, activation, dispergation directly to carry out chemical plating stannum earlier, and process step is simple, easy handling, easy to maintenance; In eleetrotinplate, use the vitriol eleetrotinplate then, composition is simple, sedimentation velocity fast (can reach 40～50 microns/hour), and current efficiency high (greater than 95%), production efficiency is high, and the plating bath environmental pollution is little; (2) foam tin material of gained have certain intensity, in light weight, specific surface area is big, through-hole rate is high, be easy to welding, tin coating purity is high, impurity is few, the coating soft texture, porosity is low; (3) after the corrosion of the foam tin material of gained, can not dissolve other metals ion, influence the chemical property of foam tin by its matrix.
Description of drawings
Fig. 1 is the preparing method's of foam tin material among the embodiment 1 a process flow sheet.
The foam tin material that Fig. 2 prepares for embodiment 1 amplifies 100 times metallograph.
The foam tin material that Fig. 3 prepares for embodiment 1 amplifies 400 times metallograph.
Embodiment
Embodiment 1: a kind of preparation method of foam tin material, and preparation process is:
(1) alligatoring: 20 * 15 * 1 centimetre polyurethane sponge is immersed in the mixing solutions of sulfuric acid 500ml/L and SRM 935a 10g/L and corroded 5 minutes;
(2) neutralization: the polyurethane sponge after the alligatoring was soaked 1 minute in the sodium hydroxide solution of 80g/L;
(3) preimpregnation: the polyurethane sponge after will neutralizing, be soaked in the presoak and soaked 30 minutes, described presoak is tin protochloride 10g/L and hydrochloric acid 40ml/L;
(4) activation: the polyurethane sponge after the preimpregnation is soaked in carried out activation treatment in the activation solution 30 minutes, activation solution is the mixed solution of tin protochloride 80g/L, Palladous chloride 0.1g/L, hydrochloric acid 300ml/L, sodium stannate 10g/L;
(5) dispergation: the polyurethane sponge after the activation is carried out dispergation handled 3 minutes in the 100ml/L hydrochloric acid soln;
(6) chemical plating stannum: with the polyurethane sponge behind the dispergation at tin protochloride 5g/L, ammonium citrate 120g/L, EDTA di-potassium 15g/L, nitrilotriacetic acid(NTA) 7g/L, titanous chloride 3.75g/L; Potassium ethanoate 20g/L; In the basic soln of pH value 8.5; 85 ℃ of chemical plating stannums 25 minutes, said titanous chloride uses the aqueous solution of 15% (weight percentage) titanous chloride;
(7) eleetrotinplate: the polyurethane sponge behind chemical plating stannum is made cathode, and pure tin plate is made anode, and in the solution of stannous sulfate 20g/L, sulfuric acid 50ml/L, acid zinc-plated additive 20ml/L, cathode current density is 1～2A/dm
2, to electroplate 150 minutes for 10～20 ℃, the zinc-plated additive of said acidity is mixed by mass ratio by Hydrocerol A, benzylideneacetone, TX10 at 5: 1: 10;
(8) passivation: the potassium bichromate solution with 100g/L soaked 10 seconds, washing, drying;
Adopt the secondary reverse-flow rinsing process to clean between above-mentioned each step.
The metallograph of the foam tin material that present embodiment obtains as shown in Figures 2 and 3; (because this product is to be base material with the polyurethane sponge; The outward appearance situation that below microscope, can only show a part of spongy tin clearly; Other part is a diplopia) as can be seen from the figure, the appearance coating of spongy tin is fine and close, atresia, coating half light.
Through the foam tin material that the foregoing description 1 obtains, its coating structure is closely careful, and outward appearance is pearl half light, interpenetrates between the hole, and integral body is tridimensional network, and thickness of coating is about 120 microns, and the aperture is 1～3 millimeter, and through-hole rate is 85～90%.Product has certain intensity, and weldability can be good.
Embodiment 2: a kind of preparation method of foam tin material, and preparation process is:
(1) alligatoring: 20 * 15 * 1 centimetre polyurethane sponge is immersed in the mixing solutions of sulfuric acid 200ml/L and chromic anhydride 30g/L and corroded 10 minutes;
(2) neutralization: the polyurethane sponge after the alligatoring was soaked 5 minutes in the sodium hydroxide solution of 100g/L;
(3) preimpregnation: the polyurethane sponge after will neutralizing, be soaked in the presoak and soaked 15 minutes, described presoak is tin protochloride 50g/L and hydrochloric acid 100ml/L;
(4) activation: the polyurethane sponge after the preimpregnation is soaked in carried out activation treatment in the activation solution 15 minutes, activation solution is the mixed solution of tin protochloride 100g/L, Palladous chloride 0.5g/L, hydrochloric acid 300ml/L, sodium stannate 8.5g/L;
(5) dispergation: the polyurethane sponge after the activation is carried out dispergation handled 15 minutes in the 150ml/L hydrochloric acid soln;
(6) chemical plating stannum: with the polyurethane sponge behind the dispergation at tin protochloride 7.5g/L, citric acid tri potassium 100g/L, EDTA di-potassium 15g/L, nitrilotriacetic acid(NTA) 7g/L, titanous chloride 2.25g/L; Potassium ethanoate 10g/L; In the basic soln of pH value 9; 90 ℃ of chemical plating stannums 15 minutes, said titanous chloride uses the aqueous solution of 15% (weight percentage) titanous chloride;
(7) eleetrotinplate: the polyurethane sponge behind chemical plating stannum is made cathode, and pure tin plate is made anode, and in the solution of stannous sulfate 20g/L, sulfuric acid 50ml/L, acid zinc-plated additive 20ml/L, cathode current density is 1～2A/dm
2, to electroplate 60 minutes for 10～20 ℃, the zinc-plated additive of said acidity is mixed by mass ratio by Hydrocerol A, benzylideneacetone, TX10 at 6: 1: 8;
(8) passivation: the potassium bichromate solution with 100g/L soaked 10 seconds, washing, drying;
Adopt the secondary reverse-flow rinsing process to clean between above-mentioned each step.
Through the foam tin material that the foregoing description 2 obtains, its coating structure is closely careful, and outward appearance is pearl half light, interpenetrates between the hole, and integral body is tridimensional network, and thickness of coating is 50 microns, and the aperture is 1～3 millimeter, and through-hole rate is 85～90%.Product has certain intensity, and weldability can be good.
Embodiment 3: a kind of preparation method of foam tin material, and preparation process is:
(1) alligatoring: 20 * 15 * 1 centimetre polyurethane sponge is immersed in sulfuric acid 100ml/L, corroded 15 minutes in the mixing solutions of chromic anhydride 10g/L and SRM 935a 5g/L;
(2) neutralization: the polyurethane sponge after the alligatoring was soaked 10 minutes in the sodium hydroxide solution of 50g/L;
(3) preimpregnation: the polyurethane sponge after will neutralizing, be soaked in the presoak and soaked 5 minutes, described presoak is tin protochloride 80g/L and hydrochloric acid 150ml/L;
(4) activation: the polyurethane sponge after the preimpregnation is soaked in carried out activation treatment in the activation solution 10 minutes, activation solution is the mixed solution of tin protochloride 100g/L, Palladous chloride 2g/L, hydrochloric acid 500ml/L, sodium stannate 10g/L;
(5) dispergation: the polyurethane sponge after the activation is carried out dispergation handled 20 minutes in the 150ml/L hydrochloric acid soln.
(6) chemical plating stannum: with the polyurethane sponge behind the dispergation at tin protochloride 7.5g/L, trisodium citrate 150g/L, EDTA disodium salt 20g/L, nitrilotriacetic acid(NTA) 7g/L, titanous chloride 3.75g/L; Sodium-acetate 25g/L; In the basic soln of pH value 9; 88 ℃ of chemical plating stannums 30 minutes, said titanous chloride uses the aqueous solution of 15% (weight percentage) titanous chloride;
(7) eleetrotinplate: the polyurethane sponge behind chemical plating stannum is made cathode, and pure tin plate is made anode, and in the solution of stannous sulfate 20g/L, sulfuric acid 50ml/L, acid zinc-plated additive 20ml/L, cathode current density is 1～2A/dm
2, to electroplate 100 minutes for 10～20 ℃, the zinc-plated additive of said acidity is mixed by mass ratio by Hydrocerol A, benzylideneacetone, TX10 at 6: 1: 6;
(8) passivation: the potassium bichromate solution with 50g/L soaked 10 seconds, washing, drying;
Adopt the secondary reverse-flow rinsing process to clean between above-mentioned each step.
Through the foam tin material that the foregoing description 3 obtains, its coating structure is closely careful, and outward appearance is pearl half light, interpenetrates between the hole, and integral body is tridimensional network, and thickness of coating is 80 microns, and the aperture is 1～3 millimeter, and through-hole rate is 85～90%.Product has certain intensity, and weldability can be good.
Claims (10)
1. the preparation method of a foam tin material; It is characterized in that: it may further comprise the steps: polyurethane sponge is carried out alligatoring, neutralization, preimpregnation, activation, dispergation successively; Then with the polyurethane sponge behind the dispergation in the pH value is 7～10 solution; Chemical plating stannum is 10～30 minutes under 80～95 ℃ of temperature, passes through eleetrotinplate at last, obtains foam tin material; Said solution comprises tin protochloride 5～10g/L; Mixture 80～the 150g/L of one or more of Hydrocerol A, Hydrocerol A sylvite, sodium citrate salt, Hydrocerol A ammonium salt; Mixture 5～the 20g/L of one or more of EDTA, EDTA sylvite, EDTA sodium salt, EDTA ammonium salt; Nitrilotriacetic acid(NTA) 5～10g/L, titanous chloride 2.25～3.75g/L, acetate 5～30g/L.
2. the preparation method of foam tin material according to claim 1; It is characterized in that: described alligatoring step is specially: polyurethane sponge was soaked in the strongly acidic solution etch 1～15 minute; Described strongly acidic solution is a kind of of following three kinds of mixed solutions: the mixed solution of being made up of sulfuric acid 100～500ml/L and SRM 935a 5～50g/L; The mixed solution of forming by chromic anhydride 10～100g/L and SRM 935a 5～50g/L, the mixed solution of forming by sulfuric acid 100～500ml/L, chromic anhydride 10～100g/L and SRM 935a 5～50g/L.
3. the preparation method of foam tin material according to claim 1 is characterized in that described neutralization procedure is specially: the polyurethane sponge after the alligatoring was soaked 1～10 minute in 50～100g/L sodium hydroxide solution.
4. the preparation method of foam tin material according to claim 1; It is characterized in that described preimpregnation step is specially: the polyurethane sponge after will neutralizing; In presoak, soaked 1～30 minute, described presoak is the mixed solution of tin protochloride 10～100g/L and hydrochloric acid 20～200ml/L.
5. the preparation method of foam tin material according to claim 1; It is characterized in that described activation step is specially: the polyurethane sponge after the preimpregnation is soaked in carried out activation treatment in the activation solution 1～30 minute, described activation solution is the mixed solution of tin protochloride 20～100g/L, Palladous chloride 0.1～5g/L, hydrochloric acid 100～500ml/L, sodium stannate 5～10g/L.
6. the preparation method of foam tin material according to claim 1 is characterized in that described dispergation step is specially: the polyurethane sponge after the activation is carried out dispergation handled 1～30 minute in 100～200ml/L hydrochloric acid soln.
7. the preparation method of foam tin material according to claim 1; The concrete steps that it is characterized in that described eleetrotinplate are: the polyurethane sponge behind chemical plating stannum is made cathode; Pure tin plate is made anode; In the solution of the inferior tin 10～50g/L of sulfur acid, sulfuric acid 50～100ml/L, acid zinc-plated additive 10～50ml/L, cathode current density is 1～2A/dm
2, electroplated 60～150 minutes for 10～20 ℃, the zinc-plated additive of said acidity by one or both mixture, benzylideneacetone, TX10 of Hydrocerol A or Citrate trianion by mass ratio (5～10): 1: (5～10) mixed preparing forms.
8. the preparation method of foam tin material according to claim 1 is characterized in that among the preparation method of described foam tin material, after the eleetrotinplate step is accomplished, carries out passivation: soaked for 5～30 seconds with 50～100g/L potassium bichromate solution, washing, drying.
9. the preparation method of foam tin material according to claim 1 is characterized in that adopting between described each step the secondary reverse-flow rinsing process to clean.
10. the preparation method of foam tin material according to claim 1 is characterized in that the foam tin material thickness of coating that the working method of said foam tin material prepares is 50～500 microns, and the aperture is 1～3 millimeter, and through-hole rate is 85～90%.
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| CN102916227B (en) * | 2012-07-31 | 2015-07-29 | 武汉银泰科技电源股份有限公司 | A kind of manufacture method of pure electric vehicle lead-carbon battery |
| CN102800898B (en) * | 2012-07-31 | 2016-09-14 | 武汉银泰科技电源股份有限公司 | A kind of manufacture method of micro hybrid vehicle lead-carbon battery |
| CN103540950B (en) * | 2013-11-05 | 2015-12-30 | 武汉银泰科技电源股份有限公司 | A kind of preparation method of porous silica lead material |
| CN105543815B (en) * | 2015-12-30 | 2021-12-28 | 吉安创德精密电子有限公司 | Method for improving conductive performance of conductive rubber |
| CN105489420A (en) * | 2015-12-30 | 2016-04-13 | 南通万德科技有限公司 | Composite of foamed rubber and metal and preparation method of composite |
| CN106757190A (en) * | 2016-11-21 | 2017-05-31 | 江苏梦得新材料科技有限公司 | A kind of electrotinning light agent solution |
| CN109267024B (en) * | 2018-11-02 | 2020-11-20 | 常德力元新材料有限责任公司 | Preparation method of foam tin material |
| CN109609795B (en) * | 2018-11-30 | 2020-11-27 | 常德力元新材料有限责任公司 | Preparation method of three-dimensional porous tin material |
| CN110003681B (en) * | 2019-04-02 | 2021-05-04 | 柳州光华科技有限公司 | Preparation method of foam tin material |
| CN110451324B (en) * | 2019-07-22 | 2021-08-03 | 常德力元新材料有限责任公司 | Roll-to-roll chemical plating system for double-layer sponge |
| WO2023181552A1 (en) * | 2022-03-24 | 2023-09-28 | 住友電気工業株式会社 | Metal porous body, nickel-zinc battery, and zinc air battery |
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| US20020094433A1 (en) * | 2001-01-17 | 2002-07-18 | Kevin Hug | Electrically conductive foam and method of preparation thereof |
| CN1392293A (en) * | 2001-06-14 | 2003-01-22 | 长沙力元新材料股份有限公司 | Foam iron alloy material, foam iron base composite material and their preparing method |
| CN1552954A (en) * | 2003-05-28 | 2004-12-08 | 江西省恒润实业发展有限公司 | Electrolytic removing method for chemical copper cladding in foamed lead-tin alloy cladding |
| DE102005010248B4 (en) * | 2005-02-28 | 2006-10-26 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for producing an open-pored metal foam body, a metal foam body produced in this way and its uses |
| CN1740216A (en) * | 2005-09-27 | 2006-03-01 | 北京理工大学 | Polyurethane foam metallizing treatment process |
| CN101092718B (en) * | 2007-04-10 | 2011-03-16 | 李萌初 | Composite material of foamed metal, and preparation method |
| CN101509085B (en) * | 2008-02-15 | 2011-01-26 | 湖南大学 | Process for producing foam nickel-molybdenum-cobalt ternary-alloy material |
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