CN1150060A - Process for preparing metal-ceramic composite film by chemical plating - Google Patents
Process for preparing metal-ceramic composite film by chemical plating Download PDFInfo
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- CN1150060A CN1150060A CN 95113919 CN95113919A CN1150060A CN 1150060 A CN1150060 A CN 1150060A CN 95113919 CN95113919 CN 95113919 CN 95113919 A CN95113919 A CN 95113919A CN 1150060 A CN1150060 A CN 1150060A
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- metal
- chemical plating
- counterdie
- composite membrane
- ceramic composite
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- 238000007747 plating Methods 0.000 title claims abstract description 46
- 239000000126 substance Substances 0.000 title claims abstract description 41
- 239000000919 ceramic Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003618 dip coating Methods 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001648 diaspore Inorganic materials 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims 1
- 229910002706 AlOOH Inorganic materials 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000001235 sensitizing effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 45
- 229910052763 palladium Inorganic materials 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 21
- 238000006722 reduction reaction Methods 0.000 description 13
- 238000000151 deposition Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002905 metal composite material Substances 0.000 description 5
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 5
- 229910001252 Pd alloy Inorganic materials 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Chemically Coating (AREA)
Abstract
A chemico-plating method for preparing compound metal-ceramic film features that the compound ceramic film whose metallic active component has been modified by in-situ modification on surface of sol particle is used as substrate film, which is directly put in chemico-plating liquid for chemical plating. The conventional sensitizing and activating steps are omitted as the active component particles on substrate film can act as catalytic active center and the nuclei of growing metal particle during chemical plating. The deposition speed of metal is increased and the deposition of metal on non-target area of substrate film is eliminated.
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 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 of preparation 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 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 metal-ceramic membrane 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
24g/lEDTA.2Na 67.2g/lNH
3.H
2O (28%) 350ml/lN
2H
4(0.1M) in 50 ℃ of table 4. chemical platings of 50ml/lPH 11.2 temperature process the deposition of metal and sedimentation time concern 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 sedimentation time concerns sedimentation time (hr) 0.5 1 1.52 2 2.5 3 deposition (mg/cm in the table 5. chemical plating process
2) 0.89 1.84 2.67 3.40 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
2When .hr. 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 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 obtain the counterdie of the ceramic composite membrane of the pre-modification of containing metal active constituent; 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 chloride 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 claim 1,2 described chemical plating methods 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 after the porous ceramics counterdie of casting technology dip-coating 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 true CN1150060A (en) | 1997-05-21 |
| CN1060094C CN1060094C (en) | 2001-01-03 |
Family
ID=5080125
Family Applications (1)
| 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 (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 |
| CN103157389A (en) * | 2011-12-14 | 2013-06-19 | 南京髙谦功能材料科技有限公司 | Method for preparing asymmetric porous metal film |
| CN103219089A (en) * | 2012-01-18 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Porous graphite or graphene/porous composite ceramic conductive material and preparation method thereof |
| CN103702748A (en) * | 2011-07-22 | 2014-04-02 | 韩国能源技术研究院 | Hydrogen-separation-membrane protection layer and a coating method therefor |
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL9101269A (en) * | 1991-07-19 | 1993-02-16 | Hoogovens Ind Ceramics | METHOD FOR MANUFACTURING 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
Cited By (8)
| 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 |
| CN103702748A (en) * | 2011-07-22 | 2014-04-02 | 韩国能源技术研究院 | Hydrogen-separation-membrane protection layer and a coating method therefor |
| CN103157389A (en) * | 2011-12-14 | 2013-06-19 | 南京髙谦功能材料科技有限公司 | Method for preparing asymmetric porous metal film |
| 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 |
| CN103219089A (en) * | 2012-01-18 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Porous graphite or graphene/porous composite ceramic conductive material and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1060094C (en) | 2001-01-03 |
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