CN109371279A - A kind of preparation method of porous silverskin - Google Patents
A kind of preparation method of porous silverskin Download PDFInfo
- Publication number
- CN109371279A CN109371279A CN201811256419.8A CN201811256419A CN109371279A CN 109371279 A CN109371279 A CN 109371279A CN 201811256419 A CN201811256419 A CN 201811256419A CN 109371279 A CN109371279 A CN 109371279A
- Authority
- CN
- China
- Prior art keywords
- workpiece
- gallium
- silverskin
- porous
- corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 66
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 238000005260 corrosion Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000002344 surface layer Substances 0.000 claims abstract description 17
- 229910000807 Ga alloy Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005275 alloying Methods 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 27
- 239000007769 metal material Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 24
- 229910052709 silver Inorganic materials 0.000 description 22
- 239000004332 silver Substances 0.000 description 22
- 239000011159 matrix material Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 10
- 239000000470 constituent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- 210000003041 ligament Anatomy 0.000 description 5
- 238000000866 electrolytic etching Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000002070 germicidal effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
Abstract
The present invention discloses a kind of preparation method of porous silverskin, belongs to porous metal material technical field.The method of the invention is that workpiece to be coated derusting, oil removing are cleaned up and dried；Electrosilvering is carried out to workpiece, certain thickness silverskin is electroplated in workpiece surface；It is put into gallium in the molten bath with heating and attemperator, heats and keeps 100-200 DEG C of temperature, making gallium is molten state in molten bath；Hot-dip gallium is carried out to workpiece, gallium atom penetrates into silvering and forms compound ζ ' phase between Ag-Ga alloy and silver-colored gallium metal；It takes out workpiece to put the workpiece in corrosive liquid, corrosion to no bubble is taken out after releasing, and is cleaned up and is dried, and the workpiece that surface layer is nanoporous silverskin is made.This method prepares Ag-Ga alloy surface layer only and needs 100-200 DEG C of holding temperature, saves the energy；This method features simple and practical process, can be mass-produced, high production efficiency.
Description
Technical field
The present invention relates to a kind of preparation methods of porous silverskin, belong to porous metal material technical field.
Background technique
Nano porous metal material is a kind of metal material with special construction, is structurally characterized in that internal with a large amount of
Three-dimensional co-continuous, and the hole and metallic framework for the nano-scale dimension being mutually communicated.The hole of nano-grade size, three-dimensional co-continuous
Open ligament/channel design and high specific surface area, make nano porous metal material show be different from tradition cause
The special performance of close material shows wide application prospect in fields such as catalysis, sensing, excitation, optics.
The metallic catalyst that tradition uses is usually supported nanoparticles, the disadvantage is that preparation process is complicated, product it is equal
One property is not easy to control, and particle agglomeration easily occurs for when catalysis, so that catalyst be made to lose activity, and is not easily recycled after, can not
Recycling, increases use cost.The nano porous metal material catalyst of non-loading type, due to having three-dimensional co-continuous
Ligament/channel design, it is thus possible to avoid inactivation, structure, the uniform component of material, and nano-porous gold caused by particle agglomeration
Category material is body phase material, is easily recycled and reuses.
Porous silverskin is plated on workpiece surface, has fastness is good, stability is good, the silver-colored dosage of reduction reaches to reduce cost
Advantage, and surface layer silverskin is nano-porous structure, can increase effective surface area, improves catalysis, germicidal efficiency and sensitivity.Nanometer
When porous silver is used as catalyst, there is good thermodynamics and mechanical stability and good plasticity, thus catalysis,
There is very big application potential in sterilization field.
The currently used method for preparing nano porous metal material mainly has template and goes alloyage.
Template, which refers to, is deposited on target metal materials on prefabricated foraminous die plate by physical/chemical method, deposition
After remove template, metal material as pattern and template class can be obtained.According to the difference of mould material, template can be thin
It is divided into emulsion polymer template, colloid crystal templating, liquid crystal templating method, biological template method and porous alumina formwork method etc..It is logical
The nano-porous structure high-sequential of template preparation is crossed, but material structure is limited by template, and preparation process is complicated, cost
Height is not suitable for mass production.
Alloyage is commonly gone to refer to using the difference in Electrode Potential between alloy constituent element in recent years, by one of alloy or more
The active constituent element selective corrosion of kind is fallen, and by the diffusion and self assembly of inertia constituent element, ultimately forms using inertia constituent element as skeleton
Ligament/channel-style nano-porous structure.By the nano porous metal material for going alloyage to prepare, ingredient and structure are uniform, tool
There is a three-dimensional ligament/channel design penetrated through, ligament/channel size is usually tens to several hundred nanometers, therefore has greatly ratio
Surface area.Go alloyage preparation process simple, cost is relatively low, is increasingly becoming most common prepares nano porous metal material in recent years
The method of material.
During going alloyage to prepare nano porous metal material, the preparation of presoma alloy is an important ring
Section.The method for commonly preparing presoma alloy is fusion casting, need to be mixed and heated each constituent element for preparing presoma alloy
Molten condition is allowed to alloying, and the method needs for each constituent element to be all heated to fusing point temperatures above, and heating temperature is high, and energy consumption is high；
And as Al, Mg, Zn isoreactivity constituent element all can be by dioxygen oxidations in air, so needing in fusion process under the above heating temperature
Special vacuum drying oven or atmosphere furnace is wanted to protect each constituent element isolation air, these equipment prices costly, lead to cost
Increase, complex procedures influence the large-scale of production.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of porous silverskin, specifically includes the following steps:
(1) it by workpiece to be coated derusting, oil removing, cleans up and dries；
(2) electrosilvering is carried out to workpiece, certain thickness silverskin is electroplated in workpiece surface；
(3) it is put into gallium in the molten bath with heating and attemperator, heats and keeps 100-200 DEG C of temperature, makes gallium
It is molten state in molten bath；
(4) to workpiece carry out hot-dip gallium, will be silver-plated after workpiece be suspended on bracket in batches, reduce bracket keep workpiece slow
It sinks in gallium liquid, gallium atom penetrates into silvering and forms Ag-Ga alloy ζ ' phase；Workpiece is taken out, gallium liquid remained on surface is cleaned out；
(5) it puts the workpiece in corrosive liquid and is corroded, corrosion to no bubble is taken out after releasing, and selective corrosion goes out surface conjunction
Gallium element in layer gold, the remaining silver atoms as inert element ultimately form the porous metals of aperture by diffusion, growth of reuniting
Structure is cleaned up and is dried, and the workpiece that surface layer is nanoporous silverskin is made.
Preferably, workpiece immerses the gallium liquid time for 30-120min in step (4) of the present invention.
Preferably, step (5) forms of corrosion can choose electrolytic etching, and electrolyte is that 1-2mol/L NaOH or HCl are molten
Liquid, electrolytic condition are as follows: using workpiece as anode, voltage 0.5-1V, electrolysis time 5-10min.
Preferably, step (5) forms of corrosion is also an option that chemical attack, the condition of corrosion are as follows: etchant solution be HCl or
H2SO4Solution, concentration 1-10mol/L, solution temperature are 60-80 DEG C.
Carrying out electrosilvering to workpiece in the method for the invention is conventional method, and certain thickness silver layer is electroplated in workpiece surface
The matrix of Ag-Ga alloy layer is prepared on surface layer as next step hot-dip gallium.
Of the present invention to carry out hot-dip gallium to workpiece, method therefor is conventional hot dip method, but need to extend workpiece leaching
Enter the time in liquid gallium, gallium is made to diffuse to form Ag-Ga alloy ζ ' phase into silver matrix, and to silver matrix growth inside, is formed certain
ζ ' the phase layer of thickness, the precursor layer to prepare porous silverskin as next step removal alloying, so must be according to pre-prepared porous
Silver film thickness, appropriate selection are immersed the time, and substantially 30-120min makes gallium atom obtain sufficient degree diffusion；Concrete technology
It is: upper extension, preheating, hot-dip gallium, arrangement, lower extension.
Compared with the prior art, the present invention has the following advantages:
(1) present invention utilizes gallium good diffusivity in silver, makes in such a way that gallium atom is spread in solid silver matrix
Standby Ag-Ga alloy surface layer, heat preservation a few hours can prepare the Ag-Ga alloy of several millimeters thicks at 100-200 DEG C, steam relative to using
Plating, vapor deposition, the methods of magnetron sputtering prepare other silver alloy surface layers, need dedicated equipment, expensive, this method is only
Common hot-dip coating installation is needed, technique is extremely simple, and equipment investment is low, save the cost；
(2) mode of this method removal alloying prepares porous silverskin, and the aperture on silverskin is tiny, can reach tens and receive to several hundred
Rice increases the specific surface area of workpiece, improves catalysis, germicidal efficiency.
(3) this method prepares Ag-Ga alloy surface layer only and needs 100-200 DEG C of holding temperature, saves the energy；It can give birth on a large scale
It produces, high production efficiency；By adjusting corrosive liquid type and concentration, the aperture of controllable porous silverskin；By changing hot-dip gallium
When temperature and soaking time, the thickness of controllable porous silverskin.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is workpiece surface section metallograph after hot-dip；
Fig. 3 is workpiece surface XRD spectrum after hot-dip；
Fig. 4 is workpiece surface XRD spectrum after corrosion；
Fig. 5 is workpiece surface scanning electron microscopic picture after corrosion.
Specific embodiment
With reference to the accompanying drawing and the specific embodiment present invention is described in further detail, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
A kind of preparation method of porous silverskin, technique as shown in Figure 1, specifically includes the following steps:
It by workpiece to be coated derusting, oil removing, cleans up and dries, electrosilvering is carried out to workpiece, 0.1mm is electroplated in workpiece surface
Thick silverskin；Be put into gallium in the molten bath for having heating and attemperator, heat and keep temperature be respectively 50 DEG C, 100 DEG C,
200 DEG C, gallium is made to be in molten state；To workpiece carry out hot-dip gallium, will be silver-plated after workpiece be suspended on bracket in batches, reduce
Bracket sinks to workpiece slowly in gallium liquid, and immersing the time is respectively 30,60,90,120 minutes, and gallium atom is made to diffuse into silver-colored plating
Layer, workpiece surface formed Ag-Ga alloy ζ ' phase, different temperatures and immerse the time under gained ζ ' phase thickness and the speed of growth see
Table 1.As can be seen from Table 1, at 100 DEG C the speed of growth of ζ ' phase up to 0.95 μm/min, it is seen that gallium atom is in silver matrix
Diffusion and splendid to the preparation speed of ζ ' phase.
Table 1 is different temperatures and ζ ' phase thickness and ζ ' the phase speed of growth is made under the immersion time
Compound concentration is the HCl solution of 1mol/L, keeps the temperature 80 DEG C, is put the workpiece in wherein, and corrosion there is no bubble to after generating
It takes out, cleans up；The workpiece that surface layer is nanoporous silverskin is made.
It is 100 DEG C, analyzed for the corresponding nanoporous silverskin of 30min, surface layer after hot-dip by hot-dip parameter
Section metallograph is as shown in Figure 2, it is seen that the reacted alloy surface for generating about 24 μ m thicks of workpiece surface after hot-dip gallium,
This layer of substance is Ag-Ga alloy ζ ' phase it can be seen from this surface layer XRD spectrum of Fig. 3；This entry material is in 1mol/L concentration
It is reduced to elemental silver after corroding in HCl solution, as shown in surface layer XRD spectrum after Fig. 4 corrosion；And Fig. 5 scanning electron microscope (SEM) photograph
Silverskin after piece display reduction is porous structure, and aperture is about 100-200nm；Other samples also have similar structure.
Embodiment 2
It by workpiece to be coated derusting, oil removing, cleans up and dries, electrosilvering is carried out to workpiece, 0.2mm is electroplated in workpiece surface
Silverskin；It is put into gallium in the molten bath for having heating and attemperator, 200 DEG C of temperature is heated and kept, melts gallium；It is right
Workpiece carry out hot-dip gallium, will be silver-plated after workpiece be suspended on bracket in batches, reduce bracket so that workpiece is slowly sunk to gallium liquid
In, immersing the time is 30 minutes, so that gallium atom is diffused into silvering and forms compound between Ag-Ga alloy and silver-colored gallium metal, passes through
Metallographic microanalysis, obtaining diffusion phase change layer ζ ' phase thickness is about 50 μm；Compound concentration is the HCl solution of 2mol/L, by workpiece
It is put into as anode and wherein carries out electrolytic etching, corrosion potentials 0.5V, etching time 10min take out simultaneously cleaning, drying later；
The workpiece that surface layer is nanoporous silverskin is made；Aperture is 50-100nm.
Embodiment 3
It by workpiece to be coated derusting, oil removing, cleans up and dries, electrosilvering is carried out to workpiece, 0.1mm is electroplated in workpiece surface
Silverskin；It is put into gallium in the molten bath for having heating and attemperator, 100 DEG C of temperature is heated and kept, melts gallium；It is right
Workpiece carry out hot-dip gallium, will be silver-plated after workpiece be suspended on bracket in batches, reduce bracket so that workpiece is slowly sunk to gallium liquid
In, immersing the time is 60 minutes, so that gallium atom is diffused into silvering and forms compound between Ag-Ga alloy and silver-colored gallium metal, passes through
Golden microscopic analysis, diffusion phase change layer thickness is about 60 μm；Compound concentration is the NaOH solution of 1mol/L, is put workpiece as anode
Enter wherein electrolytic etching, the workpiece that surface layer is nanoporous silverskin is made in corrosion potentials 1V, etching time 5min.Aperture is about
For 100nm.
In conclusion first one layer of silver is electroplated in workpiece surface in the present invention, the method for reusable heat immersion plating uses gallium element and this
Layer silver matrix alloying prepares Ag-Ga alloy ζ ' phase, and later to this ζ ' phase removal alloying, acid corrosion or electrolytic etching selectivity are rotten
Ablation falls the gallium element in ζ ' phase, and the vacancy left after gallium atom is corroded away, self assembly are filled up in remaining silver atoms diffusion
Form the surface layer silverskin of porous pattern.Preparation is gallium, side for the element that the Ag-Ga alloy surface layer presoma of removal alloying is selected
Formula is phase transformation caused by diffusion of the gallium atom in silver, and since gallium fusing point is low, only 29.8 DEG C, be liquid under room temperature,
Diffusivity in some metals is fabulous.Find that heat preservation a few hours gallium can be penetrated into silver matrix and be generated at 100 DEG C in an experiment
With a thickness of compound ζ ' phase between several millimeters of silver-colored gallium metal；Using gallium in silver good diffusivity, can be directly with hot-dip
Mode, which immerses silver in 100-200 DEG C of gallium liquid, to be diffused into gallium atom to form alloy surface in silver matrix, for removing alloy
Change prepares porous silverskin.Different from vapor deposition gallium, diffusion annealing forms alloy or magnetron sputtering for gallium original again behind silver matrix surface
Son injects the modes such as silver matrix, and hot-dip gallium simple process is convenient for extensive industrialization, high production efficiency；And do not need vapor deposition,
The Large expensives equipment such as magnetron sputtering, it is only necessary to for the molten bath of hot-dip, greatly reduce cost；Using Gallium diffusion into
Enter silver matrix and form alloy presoma, preparation temperature can be substantially reduced, be reduced to for 1000 DEG C of silver point or more as needed for founding
100-200 DEG C, coating temperature is substantially reduced, greatly the saving energy, meets the trend of energy-saving and emission-reduction, and due to preparation temperature
After degree declines to a great extent, silver will not be aoxidized with gallium because of contacting with air at 100-200 DEG C, when preparing presoma not
It needs to need vacuum drying oven or atmosphere furnace as founding to completely cut off air and prevent silver under high temperature, gallium oxidation, greatly simplified technique also saves
Saved purchase vacuum drying oven, atmosphere furnace cost, it can be achieved that high-volume streamlined produce.
Claims (4)
1. a kind of preparation method of porous silverskin, which is characterized in that specifically includes the following steps:
(1) it by workpiece to be coated derusting, oil removing, cleans up and dries；
(2) electrosilvering is carried out to workpiece, certain thickness silverskin is electroplated in workpiece surface；
(3) it is put into gallium in the molten bath with heating and attemperator, heats and keeps 100-200 DEG C of temperature, makes gallium
It is molten state in molten bath；
(4) to workpiece carry out hot-dip gallium, will be silver-plated after workpiece be suspended on bracket in batches, reduce bracket keep workpiece slow
It sinks in gallium liquid, gallium atom penetrates into silvering and forms Ag-Ga alloy ζ ' phase；Workpiece is taken out, workpiece surface residual gallium is cleaned out
Liquid；
(5) it puts the workpiece in corrosive liquid and is corroded, selective corrosion goes out gallium element in surface alloying layer, corrosion to no gas
Bubble takes out after releasing, and cleans up and dries, and the workpiece that surface layer is nanoporous silverskin is made.
2. the preparation method of porous silverskin according to claim 1, it is characterised in that: when workpiece immerses gallium liquid in step (4)
Between be 30-120min.
3. the preparation method of porous silverskin according to claim 1, it is characterised in that: step (5) forms of corrosion is that electrolysis is rotten
Erosion, electrolyte are 1-2mol/L NaOH or HCl solution, electrolytic condition are as follows: using workpiece as anode, voltage 0.5-1V, when electrolysis
Between 5-10min.
4. the preparation method of porous silverskin according to claim 1, it is characterised in that: step (5) forms of corrosion is that chemistry is rotten
Erosion, the condition of corrosion are as follows: etchant solution is HCl or H2SO4Solution, concentration 1-10mol/L, solution temperature are 60-80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811256419.8A CN109371279A (en) | 2018-10-26 | 2018-10-26 | A kind of preparation method of porous silverskin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811256419.8A CN109371279A (en) | 2018-10-26 | 2018-10-26 | A kind of preparation method of porous silverskin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109371279A true CN109371279A (en) | 2019-02-22 |
Family
ID=65390030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811256419.8A Pending CN109371279A (en) | 2018-10-26 | 2018-10-26 | A kind of preparation method of porous silverskin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109371279A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111528562A (en) * | 2020-05-18 | 2020-08-14 | 郑州机械研究所有限公司 | Nose bridge strip for mask and preparation method thereof |
| CN112159994A (en) * | 2020-09-10 | 2021-01-01 | 南京工业大学 | Superfine nano porous silver SERS substrate material based on (111) plane orientation enrichment and preparation method thereof |
| CN113881939A (en) * | 2021-10-25 | 2022-01-04 | 昆明理工大学 | Method for preparing nano porous copper by dealloying |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191400A (en) * | 2011-05-06 | 2011-09-21 | 上海大学 | Dealloying preparation method of nanoporous metal under static magnetic field |
| CN106073761A (en) * | 2016-05-28 | 2016-11-09 | 惠州市力道电子材料有限公司 | A kind of surface is provided with the matrix of nano-porous silver, its preparation method and application |
| KR101707205B1 (en) * | 2015-12-10 | 2017-02-15 | 한국기초과학지원연구원 | Method for fabricating a porous silver layer structure and method for measuring a fluorescence signal using the structure |
| CN107385372A (en) * | 2017-08-02 | 2017-11-24 | 山东大学 | A kind of preparation method of nano-structural transition metal film |
-
2018
- 2018-10-26 CN CN201811256419.8A patent/CN109371279A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191400A (en) * | 2011-05-06 | 2011-09-21 | 上海大学 | Dealloying preparation method of nanoporous metal under static magnetic field |
| KR101707205B1 (en) * | 2015-12-10 | 2017-02-15 | 한국기초과학지원연구원 | Method for fabricating a porous silver layer structure and method for measuring a fluorescence signal using the structure |
| CN106073761A (en) * | 2016-05-28 | 2016-11-09 | 惠州市力道电子材料有限公司 | A kind of surface is provided with the matrix of nano-porous silver, its preparation method and application |
| CN107385372A (en) * | 2017-08-02 | 2017-11-24 | 山东大学 | A kind of preparation method of nano-structural transition metal film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111528562A (en) * | 2020-05-18 | 2020-08-14 | 郑州机械研究所有限公司 | Nose bridge strip for mask and preparation method thereof |
| CN112159994A (en) * | 2020-09-10 | 2021-01-01 | 南京工业大学 | Superfine nano porous silver SERS substrate material based on (111) plane orientation enrichment and preparation method thereof |
| CN112159994B (en) * | 2020-09-10 | 2021-08-06 | 南京工业大学 | Superfine nano porous silver SERS substrate material based on (111) plane orientation enrichment and preparation method thereof |
| CN113881939A (en) * | 2021-10-25 | 2022-01-04 | 昆明理工大学 | Method for preparing nano porous copper by dealloying |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109371279A (en) | A kind of preparation method of porous silverskin | |
| EP2623644B1 (en) | Methods for producing a high temperature oxidation resistant MCrAlX coating on superalloy substrates | |
| Chen et al. | Fabrication and characterization of highly-ordered valve-metal oxide nanotubes and their derivative nanostructures | |
| CN104562128B (en) | A kind of method for preparing thermal protection ceramic layer on metal or metallic composite surface | |
| CN108459003A (en) | A kind of preparation method of silver nano-grain coating zinc oxide surface enhanced Raman scattering effect substrate | |
| CN112522703A (en) | Fluorine-free super-hydrophobic Zn-MOF composite coating on surface of magnesium alloy and preparation method thereof | |
| CN108193255B (en) | A kind of supported porous cuprous nano piece composite material and preparation method of nano porous copper | |
| CN107385372B (en) | A kind of preparation method of nano-structural transition metal film | |
| CN101377455A (en) | Processing fluid for preparing corrosion product film / layer cross section metallographic sample and processing method thereof | |
| CN108767277A (en) | A kind of Fe-Pd bases nano-porous materials and preparation method thereof | |
| CN107034498A (en) | A kind of preparation method of graphene steel based alloy | |
| CN105908220B (en) | A kind of method that liquid electrodeposition prepares micro-nano silver dendrite | |
| CN108950651B (en) | Preparation method of magnesium alloy surface micro-arc electrophoresis HA-containing biological composite film | |
| CN108545961A (en) | A kind of preparation method of nickel oxide nano pipe | |
| CN109778250A (en) | A method of magnetic metal nanotube is prepared by controlling electrodeposition condition | |
| CN103114267B (en) | Preparation method of steel substrate surface aluminum oxide coat | |
| CN103667795B (en) | (Ni, Pt) Al resistance to high temperature oxidation bonding layer material of active element Sc modification and preparation method thereof | |
| CN107675219A (en) | The preparation method of the grapheme foam metal of carried titanium dioxide noble metal film | |
| CN110527943B (en) | Device and method for performing anti-corrosion treatment on magnesium and magnesium alloy by using supercritical carbon dioxide | |
| CN113881939A (en) | Method for preparing nano porous copper by dealloying | |
| CN106283135A (en) | A kind of method introducing rare metal Hf element in the coating | |
| CN113278850B (en) | High-temperature-resistant titanium alloy protective coating and preparation method thereof | |
| CN1730440A (en) | Micrometer, nanometer (SiC)P surface entirely-cladding technology | |
| CN113215627A (en) | Method for preparing super-hydrophobic zinc sulfide coating on surface of stainless steel | |
| CN106086997A (en) | A kind of thermally grown Al2o3or Cr2o3membranous type M Cr Al nano-composite plate and preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190222 |
|
| RJ01 | Rejection of invention patent application after publication |