CN101899690B - 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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- CN101899690B CN101899690B CN 201010301333 CN201010301333A CN101899690B CN 101899690 B CN101899690 B CN 101899690B CN 201010301333 CN201010301333 CN 201010301333 CN 201010301333 A CN201010301333 A CN 201010301333A CN 101899690 B CN101899690 B CN 101899690B
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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, such 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 plated surface is covered with 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, such 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, namely 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+Provided by soluble nickel salt, such as single nickel salt, nickelous chloride etc.; WO
4 2+Provided by soluble tungstate salt, such as sodium wolframate, potassium wolframate etc.; Complexing agent adopts the simultaneously complexing agent of complexing nickel and tungsten, such as Trisodium Citrate, EDTA etc.Other processing condition of electroplating 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 such as current density
2All applicable; Electroplating time is then according to the alloy amount of required plating, current density, material area etc., by Faraday's law formula calculative determination; 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+Provided by soluble nickel salt, such as single nickel salt, nickelous chloride etc.; WO
4 2-Provided by soluble tungstate salt, such as sodium wolframate, potassium wolframate etc.; Complexing agent adopts the simultaneously complexing agent of complexing nickel and tungsten, such as Trisodium Citrate, EDTA etc.Other operation of electroless plating and processing condition all operation and the technique with existing chemical nickel plating are identical, are generally 35～70 ℃ such 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 pass 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 only has 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 foam iron, and its plated surface is covered with 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-Provided 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, pass into 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, whole resultant metal total amount is 550g/m
2, wherein W accounts for 0.069%.
Porous iron nickel tungsten product obtained above and foam iron bi-material 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 processing behind high temperature oxidation, latter touches namely broken substantially without intensity.
Embodiment 2
The multi-porous alloy material of present embodiment is tridimensional network, and base material is nickel foam, and its plated surface is covered with 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-Provided 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, pass into 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, whole resultant metal total amount is 550g/m
2, wherein W accounts for 1.06%.
Nickel porous tungstenalloy product obtained above and nickel foam bi-material 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 processing behind high temperature oxidation, latter's intensity reduces greatly, substantially can't test.
Embodiment 3
The multi-porous alloy material of present embodiment is tridimensional network, and base just is the nickel foam iron alloy, and its plated surface is covered with 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-Provided 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, whole resultant metal total amount is 2000g/m
2, wherein W accounts for 0.045%.
Porous iron nickel tungsten product obtained above and foam iron-nickel alloy bi-material 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 processing behind high temperature oxidation, the latter touches namely broken substantially without intensity.
Embodiment 4
The multi-porous alloy material of present embodiment is tridimensional network, and base material is foam copper, and its plated surface is covered with 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-Provided 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, whole resultant metal total amount is 4900g/m
2, wherein W accounts for 0.15%.
Porous Cu nickel tungsten product obtained above and foam copper alloy bi-material 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 processing behind high temperature oxidation, the latter touches namely broken substantially without intensity.
Embodiment 5
The multi-porous alloy material of present embodiment is tridimensional network, and base material is the nickel foam iron alloy, and its plated surface is covered with 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-Provided 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, pass into 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, whole resultant metal total amount is 2500g/m
2, wherein W accounts for 0.25%.
Porous iron nickel tungsten product obtained above and Punching steel strip bi-material 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 processing behind high temperature oxidation, the latter touches namely broken substantially without intensity.
Claims (6)
1. multi-porous alloy material is characterized in that: be tridimensional network, be covered with nickel tungsten at the plated surface of substrate porous metal material, the plating amount of described nickel tungsten is no less than 50 gram/square meters;
The preparation method of described multi-porous alloy material may further comprise the steps: (1) adopts induced codeposition plating 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;
The per-cent that the quality of tungsten accounts for the metallic substance total mass is 0.045%～1.1%.
2. multi-porous alloy material as claimed in claim 1, 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 2-4.
3. multi-porous alloy material as claimed in claim 1, 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.
4. multi-porous alloy material as claimed in claim 1 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.
5. multi-porous alloy material as claimed in claim 4 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.
6. multi-porous alloy material as claimed in claim 5, it is characterized in that: described thermal treatment temp is 300～1000 ℃.
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| WO2012077550A1 (en) * | 2010-12-08 | 2012-06-14 | 住友電気工業株式会社 | Metallic porous body having high corrosion resistance and method for manufacturing same |
| WO2012115243A1 (en) | 2011-02-24 | 2012-08-30 | 新日本製鐵株式会社 | HIGH-STRENGTH α+β TYPE HOT-ROLLED TITANIUM ALLOY WITH EXCELLENT COIL HANDLING PROPERTIES WHEN COLD, AND PRODUCTION METHOD THEREFOR |
| JP5700846B2 (en) * | 2012-03-28 | 2015-04-15 | 本田技研工業株式会社 | Internal combustion 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 |
| WO2019014223A1 (en) * | 2017-07-10 | 2019-01-17 | The University Of Akron | Catalytic metal coatings for metal components for improved tribological performance in lubricated systems |
| CN110029377B (en) * | 2019-05-15 | 2021-02-09 | 东南大学 | Long-wave-band ultra-black porous composite material and preparation method thereof |
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| CN1355097A (en) * | 2000-11-30 | 2002-06-26 | 北京有色金属研究总院 | Composite foam metal and its preparing process |
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