CN106064241A - A kind of preparation method of internal diameter controllable foam metal - Google Patents

A kind of preparation method of internal diameter controllable foam metal Download PDF

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Publication number
CN106064241A
CN106064241A CN201610541602.7A CN201610541602A CN106064241A CN 106064241 A CN106064241 A CN 106064241A CN 201610541602 A CN201610541602 A CN 201610541602A CN 106064241 A CN106064241 A CN 106064241A
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substrate
hollow
filter
deionized water
metal sphere
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CN201610541602.7A
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CN106064241B (en
Inventor
张贵峰
索妮
郑萍萍
黄昊
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Dalian University of Technology
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Dalian University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1103Making porous workpieces or articles with particular physical characteristics
    • B22F3/1112Making porous workpieces or articles with particular physical characteristics comprising hollow spheres or hollow fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/1851Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886Multistep pretreatment
    • C23C18/1893Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemically Coating (AREA)
  • Powder Metallurgy (AREA)

Abstract

The preparation method of a kind of internal diameter controllable foam metal, belongs to new structure preparation field integrated with functional material.It has main steps that: (1) pretreating process: cleans, is roughened and activates substrate;(2) chemical plating process;(3) hollow ball is prepared: sample chemical plating obtained is placed in strong base solution, removes substrate, it is thus achieved that hollow metal sphere;Cleaning, filtration, fluid-tight preserve;(4) sintering process: alternately laid with hollow metal sphere by metal nano powder, is dried, evacuation, logical protective gas, sintering temperature 1,200 1600 DEG C, annealing time 2 6h;Hollow metal sphere and metal nano powder mass ratio are 5% 30%.This method obtains, by controlling coarsening time, the substrate grain that particle diameter is different, prepares the hollow metal sphere that internal diameter is different.This technique has the advantages such as simple, convenient, economic and spherical shell internal diameter is controlled, is particularly useful for making foam metal material or the gradient multifunctional material of different inner diameters.

Description

A kind of preparation method of internal diameter controllable foam metal
Technical field
The invention belongs to new structure preparation field integrated with functional material, relate to roughening during substrate control, activation processing, Chemical plating process and remove technology, to obtain the hollow metal sphere of different inner diameters, then makes block through cold-rolled sintered, particularly to Foam metal or gradient porous functional material, it is adaptable to heat insulation, electrode, catalysis, damping, electromagnetic shielding are various with biomedical etc. High-technology field.
Background technology
Foam metal is a kind of structure-function integration material being widely studied, and has good physical and chemical performance, As little in density, specific surface area is big, material fine structure designability and optimization property good.Its hole by the airtight hole in ball and Gap between spheroid is constituted, and this unique texture makes it have the mechanics of excellence, the performance such as receives, exchanges and be combined.By extensively It is applied to the various high-technology fields such as space flight, aviation, environmental protection, the energy and biological medicine.
At present, the method preparing foam metal has casting, foaming, sintering process and sedimentation.Wherein, first three technique The shortcomings such as the foam metal of preparation, has distribution of pores and size is uneven, and mechanical property is prominent and discreteness is big;Sedimentation In electrochemical process, owing to substrate is confined to conductive material, and limited by limiting current density, therefore deposition velocity is relatively Slowly, production efficiency is low, relatively costly.But, chemical plating process is possible not only on the metallic substrate (ferrum, rustless steel, aluminum, copper etc.) Can also on nonmetallic substrate (pottery, glass, diamond, carbon plate, plastics, resin etc.) deposition metal level (as nickel, ferrum, copper, Gold, lead etc.).Without additional power source, there is not the impact that electric force lines distribution is uneven, the coating of deposition is uniform, fine and close, hole Less, hardness is high, have fabulous process based prediction model.
Roughening treatment during control, chemical plating process and substrate are removed technology and combine by the present invention, it is thus achieved that internal diameter is controlled Metal hollow ball monomer.Then being mixed with corresponding metal nanoparticle by single body hollow ball, cold-rolled sintered shaping obtains foam Metal blocks.First, by controlling different coarsening times, different-grain diameter graininess substrate is obtained (such as silica-gel desiccant, dioxy SiClx, silicon);Secondly, chemical plating is utilized to prepare metal level on non-metallic particle substrate;Strong base solution is finally utilized to remove lining The end, it is thus achieved that the metal ball of hollow structure.Substrate size (i.e. metal ball internal diameter) is determined by coarsening time, and shell thickness is by chemical plating Sedimentation time determine.So, this technique has the advantages such as simple, convenient, economic and spherical shell internal diameter is controlled, particularly suitable In the foam metal material preparing different inner diameters.
Summary of the invention
It is an object of the invention to provide a kind of technology and cold-rolled sintered of roughening treatment during control, chemical plating, substrate being removed Combine, it is thus achieved that the technique of foam metal block.And make it be applied to various high-technology field.
Technical scheme:
A kind of preparation method of internal diameter controllable foam metal, step is as follows:
(1) pretreating process
Clean substrate with acetone, ethanol and deionized water the most successively, filter and dry;Described substrate is silica dehydrator Agent, silicon dioxide or silicon;
B. substrate, is mixed to 50 DEG C with roughening agent heating in water bath respectively, keeps temperature 50 C, coarsening time 1- 5min;After end, neutralize with deionized water cleaning, ammonia, clean with deionized water again, filter and dry;
C. activating solution is added in the roughening substrate that step B obtains, soak time 5-10min, stir to it uniform, filter And dry, obtain activating substrate;
(2) chemical plating process
D. plating solution is put in thermostat water bath, be heated to temperature required;Activation substrate step C obtained is placed in plating solution Middle 1-7min, more repeatedly clean with ethanol solution with deionized water, filter and oven drying at low temperature is in order to prevent from heating up Hurry up, temperature is too high and causes film separation;
(3) hollow ball is prepared
E. the sample that step D obtains is placed in strong base solution, removes substrate, it is thus achieved that hollow metal sphere;By hollow metal Ball deionized water and ethanol solution repeatedly clean, filter, and fluid-tight preserves;
(4) sintering process
F. metal nano powder is alternately laid with hollow metal sphere, be dried, evacuation, logical protective gas, sintering temperature 1200-1600 DEG C, annealing time 2-6h;Hollow metal sphere and metal nano powder mass ratio are 5%-30%.
Beneficial effects of the present invention: can obtain in the different substrate grain of particle diameter and then preparation by controlling coarsening time The hollow metal sphere that footpath is different, it is not necessary to buy the granule substrate of different-grain diameter.This technique have simple, convenient, economical and The advantages such as spherical shell internal diameter is controlled, are particularly useful for making foam metal material or the gradient multifunctional material of different inner diameters.
Detailed description of the invention
Below in conjunction with technical scheme, further illustrate the detailed description of the invention of the present invention.
Embodiment 1:
(1) pretreating process
Clean silica-gel desiccant with acetone, ethanol and deionized water the most successively, filter and dry;
B. silica-gel desiccant and roughening agent heating in water bath respectively, to 50 DEG C, are mixed, keep temperature 50 C, during roughening Between 3min;After end, neutralize with deionized water cleaning, ammonia, clean with deionized water again, filter and dry;
C. activating solution is added in the roughening substrate that step B obtains, soak time 5min, be stirred until homogeneous, filter and dry Dry, obtain activating substrate;
(2) chemical plating process
D. nickel-plating liquid is put in thermostat water bath, be heated to 88-92 DEG C;Activation substrate step C obtained is placed in plating 3min in nickel liquid, more repeatedly clean with ethanol solution with deionized water, filter and oven drying at low temperature is in order to prevent from heating up Hurry up, temperature is too high and causes film separation;
(3) hollow ball is prepared
E. the sample that step D obtains is placed in strong base solution, removes substrate, it is thus achieved that hollow nickel sphere;Hollow nickel sphere is used Deionized water and ethanol solution repeatedly clean, filter, and fluid-tight preserves;
(4) sintering process
F. nano-nickel powder is alternately laid with hollow nickel sphere, be dried, evacuation, logical nitrogen, sintering temperature 1300 DEG C, annealing Time 5h;Hollow nickel sphere and nano-nickel powder mass ratio are 15%.
Embodiment 2:
(1) pretreating process
Clean silicon dioxide with acetone, ethanol and deionized water the most successively, filter and dry;
B. silicon dioxide and roughening agent heating in water bath respectively, to 50 DEG C, are mixed, keep temperature 50 C, coarsening time 4min;After end, neutralize with deionized water cleaning, ammonia, clean with deionized water again, filter and dry;
C. activating solution is added in the roughening substrate that step B obtains, soak time 8min, be stirred until homogeneous, filter and dry Dry, obtain activating substrate;
(2) chemical plating process
D. iron plating liquid is put in thermostat water bath, be heated to 48-52 DEG C;Activation substrate step C obtained is placed in plating 5min in ferrum liquid, more repeatedly clean with ethanol solution with deionized water, filter and oven drying at low temperature is in order to prevent from heating up Hurry up, temperature is too high and causes film separation;
(3) hollow ball is prepared
E. the sample that step D obtains is placed in strong base solution, removes substrate, it is thus achieved that hollow iron ball;With deionized water with Ethanol solution repeatedly cleans, filters, and fluid-tight preserves;
(4) sintering process
F. nanometer iron powder is alternately laid with hollow iron ball, be dried, evacuation, logical argon, sintering temperature 1400 DEG C, annealing Time 6h;Hollow iron ball and nanometer iron powder mass ratio are 20%.

Claims (2)

1. the preparation method of an internal diameter controllable foam metal, it is characterised in that step is as follows:
(1) pretreating process
Clean substrate with acetone, ethanol and deionized water the most successively, filter and dry;
B. substrate and roughening agent heating in water bath respectively are to 50 DEG C, and mixing keeps temperature 50 C, coarsening time 1-5min;After end, Neutralize with deionized water cleaning, ammonia, clean with deionized water again, filter and dry;
C. activating solution is added in the roughening substrate that step B obtains, soak time 5-10min, stir to it uniform, filter and dry Dry, obtain activating substrate;
(2) chemical plating process
D. plating solution is put in thermostat water bath, be heated to temperature required;Activation substrate step C obtained is placed in 1-in plating solution 7min, more repeatedly clean with ethanol solution with deionized water, filter and oven drying at low temperature;
(3) hollow ball is prepared
E. the sample that step D obtains is placed in strong base solution, removes substrate, it is thus achieved that hollow metal sphere;Hollow metal sphere is used Deionized water and ethanol solution repeatedly clean, filter, and fluid-tight preserves;
(4) sintering process
F. metal nano powder is alternately laid with hollow metal sphere, be dried, evacuation, logical protective gas, sintering temperature 1200- 1600 DEG C, annealing time 2-6h;Wherein, hollow metal sphere and metal nano powder mass ratio are 5%-30%.
Preparation method the most according to claim 1, it is characterised in that described substrate is silica-gel desiccant, silicon dioxide Or silicon.
CN201610541602.7A 2016-07-09 2016-07-09 A kind of preparation method of internal diameter controllable foam metal Expired - Fee Related CN106064241B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107052341A (en) * 2017-01-23 2017-08-18 郭荞毓 A kind of continuous preparation technology of advanced pore morphology foamed aluminium bead
CN109989049A (en) * 2019-04-17 2019-07-09 中国工程物理研究院激光聚变研究中心 A kind of porous metal material and preparation method thereof with hole-closing structure
CN110000375A (en) * 2019-04-17 2019-07-12 中国工程物理研究院激光聚变研究中心 A kind of superelevation porosity porous metal material and preparation method thereof
CN111842854A (en) * 2020-07-08 2020-10-30 鞍钢股份有限公司 Method and device for manufacturing heterogeneous hollow ball foam steel

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* Cited by examiner, † Cited by third party
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EP0402738A2 (en) * 1989-06-16 1990-12-19 Inco Limited Nickel foam
JPH07118713A (en) * 1993-10-22 1995-05-09 Katayama Tokushu Kogyo Kk Superfine metal granular powder, metallic porous body formed with the powder and production of the powder and metallic porous body
JPH09143509A (en) * 1995-11-16 1997-06-03 Hitachi Chem Co Ltd Production of foam
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
CN101043077A (en) * 2006-03-24 2007-09-26 中国科学院大连化学物理研究所 Application of polyporous material in sodium polysulfide/bromine accumulation energy power cell electric pole
CN101445883A (en) * 2008-12-30 2009-06-03 浙江工贸职业技术学院 Porous foam metal preparation method
CN101798222A (en) * 2010-03-02 2010-08-11 中国地质大学(北京) Al2O3-Ni-C-B4C composite ceramic and preparation method thereof
CN104607640A (en) * 2014-12-10 2015-05-13 周宏� Method for preparing block foam metal through seed-growth method
JP2015147989A (en) * 2014-02-07 2015-08-20 株式会社村田製作所 Porous metal body and method for producing the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0402738A2 (en) * 1989-06-16 1990-12-19 Inco Limited Nickel foam
JPH07118713A (en) * 1993-10-22 1995-05-09 Katayama Tokushu Kogyo Kk Superfine metal granular powder, metallic porous body formed with the powder and production of the powder and metallic porous body
JPH09143509A (en) * 1995-11-16 1997-06-03 Hitachi Chem Co Ltd Production of foam
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
CN101043077A (en) * 2006-03-24 2007-09-26 中国科学院大连化学物理研究所 Application of polyporous material in sodium polysulfide/bromine accumulation energy power cell electric pole
CN101445883A (en) * 2008-12-30 2009-06-03 浙江工贸职业技术学院 Porous foam metal preparation method
CN101798222A (en) * 2010-03-02 2010-08-11 中国地质大学(北京) Al2O3-Ni-C-B4C composite ceramic and preparation method thereof
JP2015147989A (en) * 2014-02-07 2015-08-20 株式会社村田製作所 Porous metal body and method for producing the same
CN104607640A (en) * 2014-12-10 2015-05-13 周宏� Method for preparing block foam metal through seed-growth method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107052341A (en) * 2017-01-23 2017-08-18 郭荞毓 A kind of continuous preparation technology of advanced pore morphology foamed aluminium bead
CN109989049A (en) * 2019-04-17 2019-07-09 中国工程物理研究院激光聚变研究中心 A kind of porous metal material and preparation method thereof with hole-closing structure
CN110000375A (en) * 2019-04-17 2019-07-12 中国工程物理研究院激光聚变研究中心 A kind of superelevation porosity porous metal material and preparation method thereof
CN109989049B (en) * 2019-04-17 2021-02-09 中国工程物理研究院激光聚变研究中心 Porous metal material with closed pore structure and preparation method thereof
CN110000375B (en) * 2019-04-17 2021-04-09 中国工程物理研究院激光聚变研究中心 Ultrahigh-porosity porous metal material and preparation method thereof
CN111842854A (en) * 2020-07-08 2020-10-30 鞍钢股份有限公司 Method and device for manufacturing heterogeneous hollow ball foam steel
CN111842854B (en) * 2020-07-08 2021-11-16 鞍钢股份有限公司 Method and device for manufacturing heterogeneous hollow ball foam steel

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