CN1060094C - Process for preparing metal-ceramic composite film by chemical plating - Google Patents
Process for preparing metal-ceramic composite film by chemical plating Download PDFInfo
- Publication number
- CN1060094C CN1060094C CN95113919A CN95113919A CN1060094C CN 1060094 C CN1060094 C CN 1060094C CN 95113919 A CN95113919 A CN 95113919A CN 95113919 A CN95113919 A CN 95113919A CN 1060094 C CN1060094 C CN 1060094C
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- CN
- China
- Prior art keywords
- chemical plating
- metal
- counterdie
- colloidal sol
- plating method
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5105—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the noble metals or copper
Abstract
The present invention relates to a chemical plating method for preparing a composite metal-ceramic film. In the method, a composite ceramic film for decorating metal active components, which is obtained by utilizing an in-situ decorative method on the surfaces of colloidal sol particles, is used as a basal film. The basal film is directly added to chemical plating liquid for carrying out chemical plating. Because active component particles on the basal film can be used as crystal nucleus for catalyzing the growth of an active center and metal particles in the process of chemical plating, the chemical plating method cancels the steps of sensitization and activation necessary to the process of normal chemical plating. Moreover, the chemical plating method has the functions of accelerating the deposition rate of metal and simultaneously avoiding the deposition of the metal on a non-target surface of the basal film.
Description
The present invention relates to preparation of inorganic, the ceramic composite membrane of metal active component that specifically provided modification that a kind of at first in-situ modification method by the colloidal sol surface makes, be counterdie with this composite membrane again, directly carry out the new method that chemical plating prepares the metal-ceramic composite membrane.
Inoranic membrane is owing to have good heat endurance and machinery and structural stability, the ability of anti-chemical reagent and microbial attack, easily purify, add that it has bigger finishing potentiality than organic film with the performance of regeneration, therefore it replaces traditional organic film material and has very attractive prospect as a kind of separation membrane on the one hand, exists on the other hand from the realistic possibility of inoranic membrane acquisition reaction with the new chemical materials that separates difunctional unification (catalytic membrane).Thereby the research of relevant inoranic membrane more and more is subject to people's attention.When but inoranic membrane was applied to gas and catalytic reaction, its separative efficiency was lower.Therefore, the gas separative efficiency that how to improve inoranic membrane is one of people institute focus.Because the gas permeability of inorganic porous membrane is higher, people attempt to improve the selectivity of perforated membrane to gas by the film finishing.This method is to come the modified membrane surface by introducing certain material, because this material energy is preferential and certain gas interacts, improves the infiltration diffusing capacity on film surface, thereby has improved membrane separation efficiency.Though but by introduce certain active material on the porous ceramics composite membrane, this material and some gas have stronger interaction, thereby can improve the selectivity of film to these gases.Yet in a lot of fields as needing a large amount of High Purity Hydrogen even ultra-pure hydrogen in electronics, metallurgy and the petro chemical industry, this separation of having modified the ceramic composite membrane of active material obviously can not satisfy needs high-purity and the ultra-pure hydrogen preparation, in order further to improve the selecting property earlier that film separates hydrogen, to satisfy the needs that high-purity ultra-pure hydrogen and high efficiency hydrogen separate, people concentrate on sight on the compact metal film one after another, are representative with palladium and palladium alloy membrane especially.Early stage palladium and palladium alloy membrane all are non-supported, owing to be subjected to the restriction of factors such as mechanical strength, the thickness of these palladiums and palladium alloy membrane is generally greater than 150 μ m.Because hydrogen sees through the speed and the film thickness of palladium and palladium alloy membrane and is inversely proportional to, the film thickness increase means the reduction of the saturating hydrogen speed of film, and film thickness increases simultaneously, causes metal consumption to increase, thereby causes that cost increases.The metal composite film that development in recent years goes out successfully overcomes these shortcomings, this composite membrane be by the thin metal teleblem with high saturating amount high selectivity be supported on the porous, inorganic counterdie with high thermal stability and mechanical stability and, these porous, inorganic counterdies such as stainless steel, cellular glass, pottery, porous silver etc., thus guaranteed that metal composite film not only has favorable mechanical stability but also have higher permeability.The preparation method of metal composite film also has a variety of, and close with the present invention is chemical plating method.Equipment is simple owing to having for this method, cost low and can deposit the complete teleblem of one deck on the counterdie of arbitrary shape and hardness becomes metal composite film preparation method commonly used.So-called chemical plating, for example concerning palladium, the metastable complex compound that is actually palladium is reduced the reduction of agent hydrazine hydrate and decomposes generation metallic state palladium nuclear on the substrate target surface, and these palladium nuclears just in time are the catalyst of this reduction reaction, thereby this reduction reaction with self-catalysis feature is proceeded, and palladium nuclear constantly generates, increases and the fine and close one deck of formation in substrate surface.Yet some substrates such as cellular glass, pottery even stainless steel etc. do not have enough catalytic activitys to above-mentioned reduction reaction, therefore can not start this reduction reaction quickly, need very long induction period and reduction reaction is carried out.In order to eliminate this induction period, before chemical plating, also must on the substrate target surface, form enough palladium nuclear as the activated centre, with the above-mentioned reduction reaction of catalysis.Conventional method is to obtain by pre-sensitizing activation process, yet the preprocessing process cycle of this sensitization activation is grown but also can introduce some impurity.
The object of the present invention is to provide a kind of chemical plating method for preparing the metal-ceramic composite membrane, this method can save in the conventional chemical plating process the sensitization activation step that must carry out, and the metal deposition velocity is accelerated, and has also avoided the deposition of metal on the non-target surface of counterdie simultaneously.
The chemical plating method of preparation metal-ceramic composite membrane provided by the invention, the counterdie that it is characterized in that 1. carrying out the metal-ceramic composite membrane before the chemical plating is by utilizing colloidal sol surface in situ method of modifying, make metal Pd, Rh or Ag ionic adsorption contain the oxide sol that metal component is modified to the colloidal sol surface preparation, again with this colloidal sol with casting technique dip-coating porous ceramics, the ceramic composite membrane that the metal active component of drying-roasting-reduction acquisition has been modified in advance is as counterdie; 2. be placed directly in the ceramic counterdie that contains metal composite film and carry out chemical plating in the plating bath, make the metal-ceramic composite membrane.The preparation of its chemical plating fluid and carry out the chemical plating process and can carry out according to a conventional method.The chemical plating method of preparation metal-ceramic composite membrane specifically of the present invention is pressed following step:
1. the oxide hydrosol of containing metal component preparation: adopt the in-situ modification method, be that raw material is made γ-AlOOH colloidal sol at first with water aluminium, take the metal ion of doing modification, as the nitrate or the chloride solution that contain Pd, Rh or Ag ion join in the colloidal sol, is mixed with the oxide hydrosol of metallic components;
2. dip-coating porous ceramics counterdie: utilizing casting technique, is dip-coating colloidal sol with the hydrosol of above-mentioned preparation, dip-coating porous ceramics counterdie, and drying-roasting obtains composite membrane; Above-mentioned dip-coating, drying, roasting process can repeat repeatedly, until reaching required thickness, thereby obtain the porous ceramics composite membrane of modified metal oxide;
3. use the hydrogen reduction composite membrane:, make metal ion be reduced into metallic state with the above-mentioned composite membrane of hydrogen reduction;
4. chemical plating: technology preparation chemical plating bath routinely, will be placed directly in through 3 composite membranes of handling then and carry out chemical plating in the plating bath, finish preparation metal-ceramic composite membrane.
In above-mentioned preparation method, in the hydrosol process for preparation of its containing metal component, for the metal ion major part can be adsorbed onto on the colloidal sol surface, can in pregnant solution, add complexing agent, complexing agent and complexing of metal ion, can change the charged situation of complexation of metal ions, thereby make metal ion in the scope of oxide water soluble colloid stable existence, almost completely be adsorbed onto on the surface of colloidal sol.The compound that can be used as above-mentioned complexing agent is HN
3Or contain carboxylic acid and ammonium, sodium or the sylvite of tetracarboxylic, as, EDTA or EGTA and ammonium thereof, sodium or sylvite.The proportioning of complexing agent and metal ion is 5～0.1 mol ratios.Metal component content is 0.1～20% (weight) of oxide in the oxide hydrosol of containing metal component.
In its dip-coating porous ceramics counterdie process, can in the oxide hydrosol of containing metal component, add the viscosity that an amount of polyvinyl alcohol (PVA) or polyethylene glycol (PEG) are regulated the hydrosol, be beneficial to dip-coating and carry out.Adding PVA or PEG can be according to a conventional method, and casting technique routinely, finishes dip-coating porous ceramics counterdie.Ceramic counterdie after the dip-coating carries out roasting 1～5 hour under 400～800 ℃.
Its hydrogen reduction process can be utilized the porous ceramics composite membrane of hydrogen reducing containing metal component under 200～600 ℃ of conditions.Should be no less than 30 minutes during reduction, be reduced into metal fully, be generally 0.5-4 hour in order to metal ion.Metal-ceramic composite membrane after above-mentioned processing, chemical plating method carries out chemical plating routinely, prepares the metal-ceramic film and closes film.
Describe the present invention in detail below by embodiment.
Embodiment 1
With SB powder (Germany, a kind of industrial-diaspore that Condea company produces) is γ-AlOOH colloidal sol of feedstock production 1mol/l, EDTA and Pd (NO
3)
2Be to be made into the solution of 0.01mol/l at 1: 1 in molar ratio, get certain quantity solution and join above-mentioned γ-AlOOH colloidal sol that the amount of the pd of adding is 3% (pd/ γ-Al
2O
3Percentage by weight), with the pH of acid or alkali regulation system, after the stirring, pd (II) 100% exchanges on the micelle surface, γ-AlOOH colloidal sol (weight, pd/ γ-Al that preparation 0.8mol/l 3%pd modifies
2O
3).
Embodiment 2
Set out by the SB powder,, do not prepare γ-AlOOH colloidal sol (weight, the pd/ γ-Al that 0.8mol/l1%pd modifies but do not add EDTA by the method for similar embodiment 1
2O
3), adding the viscosity that 1%PVA and 2%PRG regulate colloidal sol, the ultimate density of colloidal sol is 0.5mol/l.As dip-coating colloidal sol, dip-coating porous ceramics counterdie, counterdie are that main component is α-Al with this colloidal sol
2O
3Flat sheet membrane, its diameter is 3cm, average hole is 0.1～0.3 μ m, after the dip-coating, is placed under the room temperature dry two days, then in muffle furnace in 550 ℃ of roastings 3 hours, after dip-coating-drying-six circulations of roasting, in 500 ℃ of reduction 4 hours, the teleblem of counterdie one side became black in nitrogen atmosphere, and opposite side does not have change color, and showing does not have on the palladium distribution counterdie.
Embodiment 3
Utilize the composite membrane of embodiment 2 preparations, composite membrane is placed directly in carries out chemical plating in the plating bath, the composition of plating bath is as shown in table 3, and the deposition and the time relation of metal are as shown in table 4.The advantage of this method is to have saved sensitization activation process, and after the chemical plating, the opposite side of counterdie does not have the deposition of metal.
Table 3. chemical plating bath is formed
| Pd(NH 3) 4Cl 2 4g／l EDTA．2Na 67．2g／l NH 3．H 2O(28％) 350ml／l N 2H 4(0．1M) 50ml／l |
| 50 ℃ of PH 11.2 temperature |
The deposition of metal and the relation of sedimentation time in the table 4. chemical plating process
| Sedimentation time (hr) 0.2 0.5 1234 |
| Deposition (mg/cm 2)0．45 0．83 1．62 3．41 5．12 6．03 |
Embodiment 4
Utilize the hydrosol of the containing metal component of example 1 preparation, and make abdomen by the method for embodiment 2 and close film, wherein the content of palladium is 3% (Wt, Pd/ γ-Al
2O
3), after circulating, twice dip-coating counterdie, drying, roasting obtain γ-Al that Pd modifies with this colloidal sol then
2O
3Composite membrane, this composite membrane 500 ℃ with hydrogen reducing after 2 hours, γ-Al
2O
3Palladium on the film just is reduced into the palladium nuclear of metallic state (Pd °), then composite membrane is placed directly in and carries out chemical plating in the chemical plating liquid, the composition of the composition of plating bath such as embodiment 3 chemical plating baths, but wherein replace the pd ion with the Ag ion, the deposition and the time relation of metal are as shown in table 5, argent forms the complete teleblem of one deck on the surface of operation counterdie, thereby obtains silver/ceramic composite membrane.
The deposition of metal and the relation of sedimentation time in the table 5. chemical plating process
| Sedimentation time (hr) 0.5 1 1.5 2 2.5 3 |
| Deposition (mg/cm 2) 0．89 1．84 2．67 3．46 4．26 5．37 |
Embodiment 5
Palladium/the ceramic composite membrane of the method preparation of Application Example 3, wherein the average thickness of top layer palladium is about 5 μ m, this palladium/ceramic composite membrane is used for the hydrogen permeate experiment, wherein film high-pressure side Hydrogen Vapor Pressure is 3 atmospheric pressure (absolute pressures), low-pressure side is 1 atmospheric pressure, in the time of 500 ℃, the saturating hydrogen speed of palladium/ceramic composite membrane is 21.7m
3(STP)/m
2.hr, when using nitrogen and hydrogen mixture to carry out the gas separating experiment, the result does not detect the existence of nitrogen with the low-pressure side (being per-meate side) of gas-chromatography, illustrate that palladium/ceramic composite membrane only sees through hydrogen and do not see through nitrogen, show that also the palladium top layer is complete densification, therefore the hydrogen selective of the palladium/ceramic composite membrane of preparation can reach 100% in this way.
Show by above-mentioned example, adopt technology of the present invention saved in the conventional chemical plating process the numerous and diverse sensitization activation step consuming time of step that must carry out, and the metal deposition velocity accelerates, and also avoided the deposition of metal on the non-target surface of counterdie simultaneously.
Claims (6)
1. chemical plating method for preparing the metal-ceramic composite membrane, it is characterized in that 1) counterdie that carries out the metal-ceramic composite membrane before the chemical plating prepares by following method: at first, utilize colloidal sol surface in situ method of modifying, make metal pd, Rh or silver ion are adsorbed onto the colloidal sol surface, obtain containing the oxide sol of metal component; Use this colloidal sol again, adopt casting technique dip-coating porous ceramics counterdie, drying-roasting-reduction and the pottery that obtains the pre-modification of containing metal active constituent is protected the counterdie of film again; 2) utilize prepared counterdie, directly put into chemical plating bath and carry out chemical plating.
2. according to the described chemical plating method of claim 1, when it is characterized in that preparing the oxide hydrosol of containing metal component, complexing agent is added containing metal pd, and in the nitrate or oxide solution of Rh or silver ion, the metal ion aqueous solution that will contain complexing agent again adds in the diaspore AlOOH colloidal sol.
3. according to the described chemical plating method of claim 2, it is characterized in that complexing agent is NH
3, EDTA, EDGA or EDTA and EDGA ammonium, sodium or sylvite, complexing agent and metal ion add by 5～0.1 mol ratios.
4. according to the described chemical plating method of claim 1, it is characterized in that containing in the oxide sol of metal component tenor and oxide Al
2O
3Weight ratio be 0.1～20%.
5. according to the described chemical plating method of claim 1, it is characterized in that adopting the porous ceramics counterdie of casting technique dip-coating, under 400～800 ℃, carried out roasting 1～5 hour.
6. according to the described chemical plating method of claim 1, it is characterized in that adopting the porous of casting technique dip-coating to make pottery after the money counterdie carries out roasting, under 200～600 ℃, reduced 0.5～4 hour with hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113919A CN1060094C (en) | 1995-11-14 | 1995-11-14 | Process for preparing metal-ceramic composite film by chemical plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113919A CN1060094C (en) | 1995-11-14 | 1995-11-14 | Process for preparing metal-ceramic composite film by chemical plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1150060A CN1150060A (en) | 1997-05-21 |
| CN1060094C true CN1060094C (en) | 2001-01-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95113919A Expired - Fee Related CN1060094C (en) | 1995-11-14 | 1995-11-14 | Process for preparing metal-ceramic composite film by chemical plating |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214274A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Graphene supported porous ceramic conductive material and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101135052B (en) * | 2006-08-30 | 2010-08-18 | 中国科学院大连化学物理研究所 | Method for preparing metallic complex film |
| KR101336768B1 (en) * | 2011-07-22 | 2013-12-16 | 한국에너지기술연구원 | Protection layer of hydrogen membrane and preparation method thereof |
| CN103157389B (en) * | 2011-12-14 | 2016-03-02 | 南京髙谦功能材料科技有限公司 | A kind of preparation method of asymmetric porous metal film |
| CN103219089B (en) * | 2012-01-18 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | Porous graphene or Graphene/porous composite ceramics electric conducting material and preparation method thereof |
| CN105774171A (en) * | 2014-12-24 | 2016-07-20 | 北京有色金属研究总院 | Palladium or palladium alloy composite film on porous support surface and preparation method thereof |
| CN108117046A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of hydrogen manufacturing metal membrane reactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0524678A1 (en) * | 1991-07-19 | 1993-01-27 | Hoogovens Industrial Ceramics B.V. | Method for the manufacture of a ceramic membrane for micro or ultra filtration |
| US5186833A (en) * | 1991-10-10 | 1993-02-16 | Exxon Research And Engineering Company | Composite metal-ceramic membranes and their fabrication |
-
1995
- 1995-11-14 CN CN95113919A patent/CN1060094C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0524678A1 (en) * | 1991-07-19 | 1993-01-27 | Hoogovens Industrial Ceramics B.V. | Method for the manufacture of a ceramic membrane for micro or ultra filtration |
| US5186833A (en) * | 1991-10-10 | 1993-02-16 | Exxon Research And Engineering Company | Composite metal-ceramic membranes and their fabrication |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214274A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Graphene supported porous ceramic conductive material and preparation method thereof |
| CN103214274B (en) * | 2012-01-19 | 2015-10-28 | 中国科学院上海硅酸盐研究所 | Graphene-supported porous ceramics electro-conductive material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1150060A (en) | 1997-05-21 |
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