CN101899690A - Multi-porous alloy material and method for preparing same - Google Patents
Multi-porous alloy material and method for preparing same Download PDFInfo
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- CN101899690A CN101899690A CN201010301333XA CN201010301333A CN101899690A CN 101899690 A CN101899690 A CN 101899690A CN 201010301333X A CN201010301333X A CN 201010301333XA CN 201010301333 A CN201010301333 A CN 201010301333A CN 101899690 A CN101899690 A CN 101899690A
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Abstract
The invention provides a multi-porous alloy material and a method for preparing the same. The multi-porous alloy material has a three-dimensional network structure, and the surface of the substrate of the multi-porous alloy material is coated with nickel-tungsten alloy, wherein the tungsten accounts for no less than 0.04 percent of the total mass of the metallic material, and the coating rate of the nickel-tungsten alloy is no less than 50g/m<2>. The preparation method comprises the following steps of: coating the nickel-tungsten alloy on the surface of the common multi-porous metallic material by adopting the inducement sedimentation electroplating or chemical plating process, and performing heat treatment to obtain the finished product. The multi-porous alloy material prepared by the method has the advantages of high-temperature resistance, high strength, simple preparation process, low cost and suitability for mass production.
Description
Technical field
The present invention relates to a kind of alloy material and preparation method thereof, particularly relate to a kind of multi-porous alloy material and preparation method thereof.
Background technology
In a lot of fields, commonly used to various porous metal materials, as the nickel foam that cell base is used, the foam copper that filtering material is used etc.At tail gas clean-up base material etc. porous metal material is needed high temperature resistant and high strength Application Areas, foam tungsten is to select preferably.But because its raw materials cost is too high, and complex manufacturing technology, thereby price is high, is unfavorable for its large-scale promotion application.
Summary of the invention
The present invention aims to provide a kind of high temperature resistant, has higher-strength, and the multi-porous alloy material of low cost of manufacture and preparation method thereof.
Technical scheme of the present invention is as follows:
The present invention's multi-porous alloy material is tridimensional network, and its coating surface has nickel tungsten, and wherein the quality of the tungsten per-cent that accounts for the metallic substance total mass is no less than 0.04%; Described nickel tungsten plating amount is no less than 50 gram/square meters.
For making material both have superperformance, reduce production costs again, the quality of described tungsten accounts for the per-cent preferred 0.045%～1.1% of metallic substance total mass.
The method for preparing described multi-porous alloy material may further comprise the steps: (1) adopts known induced codeposition electrochemical plating or electroless plating method at porous metal substrate coating surface Ni-W alloy, described porous metal substrate can be selected present all kinds of conventional regular foam metallic substance for use, as nickel foam, foam iron, foam iron-nickel alloy, foam copper etc.; (2) in heat treatment furnace, the porous metal material behind the plated nickel tungstenalloy is heat-treated, promptly obtain the surface-coated multi-porous alloy material that nickel tungsten is arranged.
Described induced codeposition electrochemical plating can adopt following electroplate liquid: Ni
2+Concentration 25～70g/L, WO
4 2-Concentration 0.06～0.24mol/L, complexing agent concentration 10～100g/L adds ammoniacal liquor 20～80g/L, pH value 2～4, Ni
2+Provide by soluble nickel salt, as single nickel salt, nickelous chloride etc.; WO
4 2+Provide by soluble tungstate salt, as sodium wolframate, potassium wolframate etc.; Complexing agent adopts the complexing agent of complexing nickel and tungsten simultaneously, as Trisodium Citrate, EDTA etc.Galvanized other processing condition are identical with the condition of existing electronickelling, can be according to the size of material and the practical situation such as size of used power rectifier, 2～40A/dm as current density
2All applicable; Electroplating time is then according to the alloy amount of required plating, current density, material area etc., calculates by the Faraday's law formula and determines; Temperature of electroplating solution is generally 35～70 ℃.
Chemical plating solution is: Ni
2+Concentration 2～7g/L, WO
4 2-Concentration 0.03～0.24mol/L, complexing agent concentration 10～100g/L adds ammoniacal liquor 10～80g/L, pH value 6～10, Ni
2+Provide by soluble nickel salt, as single nickel salt, nickelous chloride etc.; WO
4 2-Provide by soluble tungstate salt, as sodium wolframate, potassium wolframate etc.; Complexing agent adopts the complexing agent of complexing nickel and tungsten simultaneously, as Trisodium Citrate, EDTA etc.Other operation of electroless plating and processing condition all operation and the technology with existing chemical nickel plating are identical, are generally 35～70 ℃ as the chemical plating fluid temperature.
Described heat-treating methods can be selected a kind of in following manner: the one, have in the heat treatment furnace can the reducing metal atmosphere, be feed in the heat treated stove can the reducing metal gas, this gas is generally the mixed gas that comprises reducing gas hydrogen and shielding gas or has only reducing gas hydrogen; The 2nd, adopt vacuum heat-treating method; Thermal treatment temp can be 300～1000 ℃, and the selection of heat treatment time is not particularly limited, and only need make material surface have metalluster non-oxidation phenomenon and get final product, and generally speaking, heat treatment time is 0.5～4 hour.
Compared with prior art, the present invention has following advantage: 1, multi-porous alloy material of the present invention is because its surface is covered with nickel tungsten, make it have good high temperature oxidation resisting effect, experiment shows, product is incubated 2h under 900 ℃ high temperature, its oxidation weight gain rate is less than 3%, and still can keep good intensity.Therefore be suitable for very much automobile exhaust gas purifying installation; 2, the present invention adopts induced codeposition electrochemical plating or electroless plating method plated nickel tungstenalloy, and compared to the sizing process that is coated with of foam tungsten, simple to operate, cost is low, and being evenly distributed of tungsten.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The multi-porous alloy material of present embodiment is tridimensional network, and base material is a foam iron, and its coating surface has nickel tungsten, and wherein to account for the per-cent of metallic substance total mass be 0.069% to the quality of tungsten; Described nickel tungsten plating amount is 50 gram/square meters.
Preparation: at thick 3mm, 60PPI, area density (amount of metal on the unit surface) 500g/m
2The surface of foam iron base material, adopt induced codeposition method electroplated Ni-W alloy, electroplate liquid is: Ni
2+Concentration is 50g/L, WO
4 2-Be 0.12mol/L, Trisodium Citrate 60g/L adds ammoniacal liquor 30g/L, and the pH value is 2.5, Ni
2+WO is provided by single nickel salt
4 2-Provide by sodium wolframate.Current density is 10A/dm
2, temperature is 50 ℃, the amount of plated nickel tungstenalloy reaches 50g/m
2After stop to electroplate.Work in-process after electroplating are placed heat treatment furnace, feed the gas mixture of hydrogen and nitrogen in the stove, thermal treatment temp is 500 ℃, and the time is 1 hour.Be tridimensional network through above-mentioned operation gained porous iron nickel tungsten product, the whole prod total metal content is 550g/m
2, wherein W accounts for 0.069%.
Two kinds of materials of the above-mentioned porous iron nickel tungsten product that obtains and foam iron are incubated 2h simultaneously under 900 ℃ high temperature in the retort furnace, the former oxidation weight gain rate is about 2.8%, less than 3%, the latter is then up to 36.7%, and the former still can maintain the strength level before handling behind high temperature oxidation, the latter does not then have intensity substantially, touches promptly broken.
Embodiment 2
The multi-porous alloy material of present embodiment is tridimensional network, and base material is a nickel foam, and its coating surface has nickel tungsten, and wherein to account for the per-cent of metallic substance total mass be 1.06% to the quality of tungsten; Described nickel tungsten plating amount is 130 gram/square meters.
Preparation: at thick 1.6mm, 110PPI, area density (amount of metal on the unit surface) 420g/m
2The surface of nickel foam base material, adopt induced codeposition method electroplated Ni W alloy, electroplate liquid is: Ni
2+Concentration is 40g/L, WO
4 2-Be 0.24mol/L, EDTA 30g/L adds ammoniacal liquor 50g/L, and the pH value is 3, Ni
2+WO is provided by nickelous chloride
4 2-Provide by potassium wolframate.Current density is 20A/dm
2, temperature is 40 ℃, the amount of plated nickel tungstenalloy reaches 130g/m
2After stop to electroplate.Work in-process after electroplating are placed heat treatment furnace, feed the gas mixture of hydrogen and nitrogen in the stove, thermal treatment temp is 1000 ℃, and the time is 0.5 hour.Be tridimensional network through above-mentioned operation gained nickel porous tungstenalloy product, the whole prod total metal content is 550g/m
2, wherein W accounts for 1.06%.
Two kinds of materials of the above-mentioned nickel porous tungstenalloy product that obtains and nickel foam are incubated 2h simultaneously under 900 ℃ high temperature in the retort furnace, the former oxidation weight gain rate is about 1.8%, less than 3%, the latter is then up to 12.5%, and the former still can maintain the strength level before handling behind high temperature oxidation, latter's intensity reduces greatly, can't test substantially.
Embodiment 3
The multi-porous alloy material of present embodiment is tridimensional network, and base just is the nickel foam iron alloy, and its coating surface has nickel tungsten, and wherein to account for the per-cent of metallic substance total mass be 0.045% to the quality of tungsten; Described nickel tungsten plating amount is 300 gram/square meters.
Preparation: at thick 10mm, 10PPI, area density (amount of metal on the unit surface) 1700g/m
2The surface of nickel porous iron alloy base material, adopt induced codeposition method electroplated Ni-W alloy, electroplate liquid is: Ni
2+Concentration is 60g/L, WO
4 2-Be 0.18mol/L, Trisodium Citrate 100g/L adds ammoniacal liquor 80g/L, and the pH value is 4, Ni
2+WO is provided by single nickel salt
4 2-Provide by potassium wolframate.Current density is 15A/dm
2, temperature is 60 ℃, the amount of plated nickel tungstenalloy reaches 300g/m
2After stop to electroplate.Work in-process after electroplating are placed vacuum heat treatment furnace, and thermal treatment temp is 300 ℃, and the time is 4 hours.Be tridimensional network through above-mentioned operation gained porous iron nickel tungsten product, the whole prod total metal content is 2000g/m
2, wherein W accounts for 0.045%.
Two kinds of materials of the above-mentioned porous iron nickel tungsten product that obtains and foam iron-nickel alloy are incubated 2h simultaneously under 900 ℃ high temperature in the retort furnace, the former oxidation weight gain rate is about 2.4%, less than 3%, the latter is then up to 18.7%, and the former still can maintain the strength level before handling behind high temperature oxidation, the latter does not have intensity substantially, touches promptly broken.
Embodiment 4
The multi-porous alloy material of present embodiment is tridimensional network, and base material is a foam copper, and its coating surface has nickel tungsten, and wherein to account for the per-cent of metallic substance total mass be 0.15% to the quality of tungsten; Described nickel tungsten plating amount is 500 gram/square meters.
Preparation: at thick 10mm, 40PPI, area density 4400g/m
2The surface of foam copper base material, adopt the Electroless Plating Ni W alloy, chemical plating fluid is: Ni
2+Concentration is 5.6g/L, WO
4 2-Be 0.12 mol/L, Trisodium Citrate 60g/L adds ammoniacal liquor 30g/L, and the pH value is 8, Ni
2+WO is provided by single nickel salt
4 2-Provide by sodium wolframate.Temperature is 45 ℃, and the amount of plated nickel tungstenalloy reaches 500g/m
2After stop.Work in-process after the electroless plating are placed vacuum heat treatment furnace, and thermal treatment temp is 300 ℃, and the time is 4 hours.Be tridimensional network through above-mentioned operation gained porous iron nickel tungsten product, the whole prod total metal content is 4900g/m
2, wherein W accounts for 0.15%.
Two kinds of materials of the above-mentioned porous copper nickel tungsten product that obtains and foam copper alloy are incubated 2h simultaneously under 900 ℃ high temperature in the retort furnace, the former oxidation weight gain rate is about 1.9%, less than 3%, the latter is then up to 25.7%, and the former still can maintain the strength level before handling behind high temperature oxidation, the latter does not have intensity substantially, touches promptly broken.
Embodiment 5
The multi-porous alloy material of present embodiment is tridimensional network, and base material is the nickel foam iron alloy, and its coating surface has nickel tungsten, and wherein to account for the per-cent of metallic substance total mass be 0.25% to the quality of tungsten; Described nickel tungsten plating amount is 800 gram/square meters.
Preparation: at thick 10mm, 10PPI, area density (amount of metal on the unit surface) 1700g/m
2The surface of nickel porous iron alloy base material, adopt Electroless Plating Ni-W alloy, chemical plating fluid is: Ni
2+Concentration is 7g/L, WO
4 2-Be 0.24mol/L, Trisodium Citrate 100g/L adds ammoniacal liquor 80g/L, and the pH value is 8, Ni
2+WO is provided by nickelous chloride
4 2-Provide by sodium wolframate.Temperature is 70 ℃, and the amount of plated nickel tungstenalloy reaches 800g/m
2After stop.Work in-process after the electroless plating are placed heat treatment furnace, feed the gas mixture of hydrogen and nitrogen in the stove, thermal treatment temp is 800 ℃, and the time is 1 hour.Be tridimensional network through above-mentioned operation gained porous iron nickel tungsten product, the whole prod total metal content is 2500g/m
2, wherein W accounts for 0.25%.
Two kinds of materials of the above-mentioned porous iron nickel tungsten product that obtains and Punching steel strip are incubated 2h simultaneously under 900 ℃ high temperature in the retort furnace, the former oxidation weight gain rate is about 2%, less than 3%, the latter is then up to 18.7%, and the former still can maintain the strength level before handling behind high temperature oxidation, the latter does not have intensity substantially, touches promptly broken.
Claims (10)
1. multi-porous alloy material is characterized in that: be tridimensional network, at the coating surface of substrate porous metal material nickel tungsten arranged, wherein the quality of the tungsten per-cent that accounts for the metallic substance total mass is no less than 0.04%.
2. multi-porous alloy material as claimed in claim 1 is characterized in that: the plating amount of described nickel tungsten is no less than 50 gram/square meters.
3. multi-porous alloy material as claimed in claim 1 or 2 is characterized in that: the per-cent that the quality of tungsten accounts for the metallic substance total mass is 0.045%～1.1%.
4. the preparation method of the described multi-porous alloy material of one of claim 1-3 is characterized in that: may further comprise the steps: (1) adopt induced codeposition electroplate or chemical plating method at porous metal substrate coating surface Ni-W alloy; (2) in heat treatment furnace, the multi-porous alloy material behind the plated nickel tungstenalloy is heat-treated.
5. as the preparation method of multi-porous alloy material as described in the claim 4, it is characterized in that: described induced codeposition is electroplated the electroplate liquid that adopts following condition: Ni
2+Concentration 25～70g/L, WO
4 2-Concentration 0.06～0.24mol/L, complexing agent concentration 10～100g/L adds ammoniacal liquor 20～80g/L, pH value 24.
6. as the preparation method of multi-porous alloy material as described in the claim 4, it is characterized in that: described chemical plating solution is: Ni
2+Concentration 2～7g/L, WO
4 2-Concentration 0.03～0.24mol/L, complexing agent concentration 10～100g/L adds ammoniacal liquor 10～80g/L, pH value 6～10.
7. as the preparation method of multi-porous alloy material as described in one of claim 46, it is characterized in that: heat-treating methods is selected from a kind of in the following method: the atmosphere of reducible metal is arranged in the heat treatment furnace, or adopt vacuum heat-treating method.
8. as the preparation method of multi-porous alloy material as described in the claim 7, it is characterized in that: the atmosphere of described reducible metal is a kind of in the following gas: the mixed gas of reducing gas hydrogen and shielding gas, or reducing gas hydrogen.
9. as the preparation method of one of claim 4-6 described multi-porous alloy material, it is characterized in that: described thermal treatment temp is 300～1000 ℃.
10. the preparation method of multi-porous alloy material as claimed in claim 7, it is characterized in that: described thermal treatment temp is 300～1000 ℃.
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| EP2650393A4 (en) * | 2010-12-08 | 2015-02-25 | Sumitomo Electric Industries | Metallic porous body having high corrosion resistance and method for manufacturing same |
| CN105220114A (en) * | 2015-10-01 | 2016-01-06 | 无棣向上机械设计服务有限公司 | Metal composite and preparation method thereof |
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| CN110029377A (en) * | 2019-05-15 | 2019-07-19 | 东南大学 | A kind of long-wave band blacker-than-black is composite porous and preparation method thereof |
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| CN1314533C (en) * | 2000-11-30 | 2007-05-09 | 北京有色金属研究总院 | Composite foam metal and its preparing process |
| CN101092718B (en) * | 2007-04-10 | 2011-03-16 | 李萌初 | Composite material of foamed metal, and preparation method |
| CN101498014B (en) * | 2008-12-31 | 2011-03-23 | 淄博圣源纳菲尔钨合金表面工程有限公司 | Electroplating process for metallic surface wear-resistance coating |
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| EP2650393A4 (en) * | 2010-12-08 | 2015-02-25 | Sumitomo Electric Industries | Metallic porous body having high corrosion resistance and method for manufacturing same |
| KR101832251B1 (en) * | 2010-12-08 | 2018-02-26 | 스미토모덴키고교가부시키가이샤 | Highly corrosion-resistant porous metal body and method for producing the same |
| US10164262B2 (en) | 2010-12-08 | 2018-12-25 | Sumitomo Electric Industries, Ltd. | Method for producing a porous metal body |
| US9850564B2 (en) | 2011-02-24 | 2017-12-26 | Nippon Steel & Sumitomo Metal Corporation | High-strength α+β titanium alloy hot-rolled sheet excellent in cold coil handling property and process for producing the same |
| CN103361638A (en) * | 2012-03-28 | 2013-10-23 | 本田技研工业株式会社 | An internal combustion engine |
| CN103361638B (en) * | 2012-03-28 | 2016-03-09 | 本田技研工业株式会社 | Oil engine |
| CN105220114A (en) * | 2015-10-01 | 2016-01-06 | 无棣向上机械设计服务有限公司 | Metal composite and preparation method thereof |
| CN110892051A (en) * | 2017-07-10 | 2020-03-17 | 阿克伦大学 | Catalytic metal coating for metal components in lubrication systems to improve friction performance |
| CN110029377A (en) * | 2019-05-15 | 2019-07-19 | 东南大学 | A kind of long-wave band blacker-than-black is composite porous and preparation method thereof |
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Effective date of registration: 20160628 Address after: Lotus pond neighborhood 415000 Changde city in Hunan Province Economic and Technological Development Zone Changde Hill Street office fourteen groups Patentee after: Changde Liyuan New Material Co., Ltd. Address before: 410100 No. 16, Xingsha Avenue, Changsha economic and Technological Development Zone, Changsha, Hunan Patentee before: Changsha Liyuan New Material Co., Ltd. |