CN101285203A - Pd-containing plating solution and uses thereof - Google Patents
Pd-containing plating solution and uses thereof Download PDFInfo
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- CN101285203A CN101285203A CNA2007100971301A CN200710097130A CN101285203A CN 101285203 A CN101285203 A CN 101285203A CN A2007100971301 A CNA2007100971301 A CN A2007100971301A CN 200710097130 A CN200710097130 A CN 200710097130A CN 101285203 A CN101285203 A CN 101285203A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
- C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
Abstract
The invention relates to palladium-bearing plating solution and a method for providing a palladium film or a palladium alloy film on a porous metal carrier. The method utilizes the electroplating method to prepare the palladium film or the palladium alloy film which uses porous metals as carrier, and can shorten the process time and simplify preparation procedures; simultaneously, the palladium film or the palladium alloy film prepared by the method has excellent compactness, good hydrogen brittleness resistance and high applicability.
Description
Technical field
Relevant Pd-containing plating solution of the present invention and the method for preparing the palladium or the palladium alloy membrane of porous metal carrier with electrochemical plating, the palladium or the palladium alloy membrane of high tack can be provided on the porous metal carrier, be used to provide the palladium film pipe fitting of the catalyst reactor of hydrogen purification or synthetic usefulness.
Background technology
The preparation of relevant palladium or palldium alloy film, known technology is to carry out with electroless plating method (electroless), vacuum splashing and plating (sputtering) or cold-rolling practice (cold-rolled) at present.Wherein, electroless plating method technology is all adopted in relevant palladium or palladium alloy membrane plating on the porous metal carrier traditionally, shows as Taiwan patent announcement I232888 number and No. 6152987 Teaching-with of institute of United States Patent (USP).Yet, electroless plating method be rely on metal particle after the chemical reduction on base material physical adsorption and adhere to plated film, sticking power between plated film and porous metal carrier is not strong, so prepared palladium or palladium alloy membrane are in use for some time often, the variation that Yin Wendu is cold and hot and on the porous metal carrier, peeling off.Moreover, be example with preparation palladium film, electroless plating method must repeat repeatedly the deposition step of (6 times～more than 7 times), can obtain the palladium film of the desired thickness of tool, just finishes after thermal treatment (annealing) homogenizing more thereafter.On the other hand, when desire prepares palladium alloy membrane, because of wayward different positively charged ions (as palladium ion, cupric ion, and silver ions) reduction/sedimentation velocity, so after need utilizing repeatedly the single ionic reduce deposition to form individual metal, again in high temperature down through long thermal treatment (annealing), to finish the metal of alloying layer that contains two kinds or multiple metal.This promptly, preparation speed is slowly, sticking power is strong obviously is disadvantage on the electroless plating method preparation procedure.
Be provided in the palladium film on the porous metal carrier with electroless plating method except that above-mentioned, Japan speciallys permit out hope, and to disclose 2002-119834 number be carrier with then disclosing with the porous ceramics for 2002-153740 number, provides palladium or palladium alloy membrane thereon with electroless plating method.Because the surface of porous ceramics or glass carrier is very careful, its hole belongs to nano level micropore (10 nanometer to 200 nanometer), so the plating sealing of hole degree of difficulty of palladium or palladium alloy membrane is relatively low, so the preferable plating film of availability matter.Yet, nano level porous carrier material price costliness, manufacturing cost is high, makes that the competitiveness of its product is not high.
Relevant palladium that carries out with the vacuum splashing and plating method or palladium alloy membrane preparation, because of its related vacuum apparatus and sputtered target material are quite expensive, and manufacturing cost remains high, so competitiveless on market.
As for the preparation of the palladium that is carried out with cold-rolling practice or palladium alloy membrane, because cold-rolling practice must be managed the gained film attached on the porous carrier, related formality is complicated and film adhesion is not strong, the processing breakage rate is also high, so also not attractive.
Present known palladium or palladium alloy membrane electroplating technology are to be applied on the general smooth carrier mostly, mainly to process or to be modified to purpose; For example, the palladium plating on this flat surface or the technology of palladium alloy membrane are normally for preventing the oxidation stain as ornaments surfaces such as jewelry, or be used for electronic component to help the element weldability, to reduce contact resistance and surface oxidation-resistant, formed coating film thickness is approximately 0.3 millimeter to 2 millimeters, as No. the 4486274th, United States Patent (USP) disclose.Yet when the palladium salt electroplate liquid formulation that this known electric coating technology is adopted is applied to the plating of porous metal carrier, can't obtain a densification, flawless palladium or palladium alloy membrane coating.In fact, can spread all over some pores on the plated film that is obtained, the purification elements of high-purity hydrogen can't be provided in order to the assembling purifying.
Therefore, the industry ubiquity be able to comparatively simple and easy, save time and economic mode forms the demand of palladium or palladium alloy membrane with desired compactness and hydrogen permeability on the porous metal carrier.
Summary of the invention
A purpose of the present invention is to provide a kind of Pd-containing plating solution, and it comprises palladous sulfate, an active conduction salt, a misfit agent, reaches a buffer reagent.
Another object of the present invention is to provide a kind of method that palladium or palladium alloy membrane are provided on the porous metal carrier, it comprises: a porous metal carrier is provided; And use a Pd-containing plating solution on this porous metal carrier, to electroplate a palladium or palladium alloy membrane.Wherein, this Pd-containing plating solution comprises a palladium salt, an active conduction salt, a misfit agent, reaches a buffer reagent.
Another purpose of the present invention is to provide a kind of complex body that contains palladium or palladium alloy membrane, and it comprises a porous metal base material; One medium layer is overlying on this substrate surface; And a palladium or a palladium alloy membrane, be overlying on this medium layer.Still there is not the phenomenon of peeling off when wherein, this palladium or the palladium alloy membrane pressure that is higher than this palladium or palladium alloy membrane side in the pressure of this complex body base material side reaches 3 bar absolute pressures in fact.
Description of drawings
Fig. 1 shows a kind of schema of method for preparing the palladium film of porous metal carrier according to the present invention with electrochemical plating;
Fig. 2 be according to the present invention under the different carriers rotating speed electron microscope picture of palladium plating film (A:10rpm, B:20rpm, C:50rpm, D:100rpm, E:500rpm);
Fig. 3 A is the electron microscope picture of the palladium plating alloy film according to the present invention;
Fig. 3 B is the analysis of components result curve figure of the palladium plating alloy film according to the present invention;
Fig. 4 is the electron microscope picture according to of the present invention two stage palladium plating films;
Fig. 5 is the synoptic diagram that shows a kind of palladium film casing reactor;
Fig. 6 is the photo copy that shows the hydrogen embrittlement test result of existing electroless plating palladium film;
Fig. 7 is the photo copy that shows the hydrogen embrittlement test result of palladium plating film of the present invention; And
Fig. 8 shows a kind of synoptic diagram that utilizes the reactor of palladium film of the present invention.
Embodiment
The invention provides a kind of Pd-containing plating solution, it comprises palladous sulfate, a kind of active conduction salt, a kind of misfit agent, reaches a kind of buffer reagent.Wherein, the palladous sulfate content in the electroplate liquid is 2 grams per liter to 200 grams per liters (calculating with palladium), is preferably 5 grams per liter to 50 grams per liters (calculating with palladium); The content of active conduction salt is 10 grams per liter to 200 grams per liters, is preferably 70 grams per liter to 150 grams per liters; The content of misfit agent is 10 grams per liter to 150 grams per liters, is preferably 30 grams per liter to 70 grams per liters; And the content of buffer reagent is to make the pH value of this electroplate liquid 9 to 12, is preferably 10 to 11.
In Pd-containing plating solution of the present invention, active conduction salt can provide conductive ion, increases the conductance of plating bath, to improve the sedimentation effect and the quality of palladium or palladium alloy membrane.The activity conduction salt that is suitable for comprises the compound that sulfate ion can be provided, and also can adopt the compound that is selected from following group: the salt of IA family metal, ammonium salt and combination thereof.Wherein, when conducting salt as activity, can increase the conductance of plating bath on the one hand, also can help the palladous sulfate dissolving of low solubility on the other hand,, further improve electrical efficiency to increase the palladium concentration in the plating bath with the compound that sulfate ion can be provided.For example (but not as limit), the used active conduction salt of the present invention can be selected from following group: sodium-chlor, Repone K, sodium sulfate, ammonium sulfate, ammonium chloride, Sulfothiorine, ammonium thiosulfate, ammonium citrate and combination thereof.Preferably, be to select for use ammonium sulfate to conduct salt as activity.
As be familiar with known to the present technique personnel, the purpose of adding the misfit agent mainly is for increasing the stability of electroplating system.Generally speaking, the misfit agent that can be used among the present invention is to be selected from following group: and boric acid, phosphoric acid salt, hypophosphite, nitrate, tartrate, Citrate trianion, edetate (ethylenediaminetetracetate, EDTA) and combination.Wherein, normally used edetate is the IA family metal-salt and/or the IIA family metal-salt of ethylenediamine tetraacetic acid (EDTA).For example (but not as limit) can adopt the misfit agent that is selected from following group: boric acid, sodium phosphate, sodium hydrogen phosphate, Hypophosporous Acid, 50 hydrogen sodium, SODIUMNITRATE, saltpetre, Seignette salt, Trisodium Citrate, Tripotassium Citrate, ammonium citrate, disodium EDTA (EDTA-Na
2), tetrasodium salt of EDTA (EDTA-Na
4), EDTA Dipotassium salt (EDTA-K
2), ethylenediamine tetraacetic acid (EDTA) tripotassium salt (EDTA-K
3), ethylenediamine tetraacetic acid (EDTA) magnesium salts (EDTA-Mg) and the combination; Be preferably and be selected from saltpetre, ammonium citrate, disodium EDTA (EDTA-Na
2), tetrasodium salt of EDTA (EDTA-Na
4) and combination.
Buffer reagent in the Pd-containing plating solution of the present invention is in order to reduce the sedimentation rate of palladium; Specifically, metallic palladium is a noble metal, and its standard electrode potential is (that is, its reduction reaction is quite fast) up to 0.997 volt.Be with, for controlling whole electroplating technology, normally in electroplate liquid, add buffer reagent to slow down the reduction reaction of metallic palladium, make it on carrier, form uniform palladium or palladium alloy membrane.Generally speaking, hydroxide ion all can reach desired buffering effect, so suitable oxyhydroxide all can be used as buffer reagent of the present invention.For example (but not as limit), can adopt the oxyhydroxide that is selected from following group is the buffer reagent of Pd-containing plating solution of the present invention: sodium hydroxide, potassium hydroxide, ammonium hydroxide and combination thereof.Preferably, be in electroplate liquid of the present invention, to use ammonium hydroxide.
Except that mentioned component, can optionally in Pd-containing plating solution of the present invention, add sulfuric acid in addition, to help the palladous sulfate dissolving.In this, the vitriolic addition is relevant with the palladous sulfate consumption.Generally speaking, the vitriolic addition is every liter of electroplate liquid to be contained have an appointment 0.2 mole to 4 moles sulfuric acid, is preferably about 0.5 mole to 2 moles sulfuric acid.
Pd-containing plating solution of the present invention also can be used for the electroplating deposition palladium alloy membrane, in this, is the salt that further comprises corresponding metal (second metal) in Pd-containing plating solution, for example: mantoquita, silver salt, golden salt, nickel salt, platinum salt, indium salt and combination thereof.Wherein, the content of the salt of this second metal change to some extent with the difference of this second metal species.In of the present invention one concrete enforcement in the aspect, be in palladium electroplating liquid, to contain mantoquita in addition, so that the palladium-copper alloy film to be provided; In this, can adopt mantoquita as copper sulfate or cupric chloride, its usage quantity can be the amount that makes copper and restrains to the scopes of 100 grams at every liter of plating bath about 0.2.Under the situation of adding second metal-salt, above-mentioned misfit agent is except that the stability that can increase plating bath, metal that also can higher with reduction potential (or lower) forms the misfit thing, its standard electrode potential is reduced (or raising), the reduction potential of two kinds of metals furthers, in carrier surface, form uniform palladium alloy membrane with common deposited.
The present invention provides a kind of method that a palladium or palladium alloy membrane are provided in addition on the porous metal carrier, it comprises: a porous metal carrier is provided; And on this porous metal carrier, electroplate a palladium or palladium alloy membrane with a Pd-containing plating solution, this Pd-containing plating solution comprises: a kind of palladium salt, content are 2 grams per liter to 200 grams per liters (calculating with palladium); A kind of active conduction salt, content is 10 grams per liter to 200 grams per liters; A kind of misfit agent, content are 10 grams per liter to 150 grams per liters; And a kind of buffer reagent, content is to make the pH value of plating bath 9 to 12.
According to the inventive method, can use any porous metal carrier, for example (but being not limited to) iron, iron alloy, copper, copper alloy, nickel, nickelalloy and combination thereof are preferably the use iron alloy.Based on considering on the economic benefit, the best is to adopt the porousness stainless steel that belongs to iron alloy for electroplating carrier.
In the inventive method, the electroplating operations of this palladium or palladium alloy membrane is in 0.01A/dm
2To 1.5A/dm
2, preferable in 0.2A/dm
2To 1.0A/dm
2Current density in the scope is carried out, and the temperature of controlling the palladium plating bath simultaneously in 40 degree Celsius to 70 degree, preferable 40 degree are to 60 degree.In addition, can rotate this metallic carrier during electroplating, its velocity of rotation generally is not to be higher than 1000rpm.
Except that palladous sulfate, electro-plating method of the present invention also can adopt the palladium salt that is selected from following group: dichloro four ammonium palladiums, ammonium chloride palladium, Palladous chloride and combination thereof.Palladium salts contg in the electroplate liquid is every liter of plating bath, and in palladium, 2 grams are to 200 grams, and preferable 5 grams are to 50 grams.Kind and consumption as for activity conduction salt, misfit agent and buffer reagent can repeat no more in this with reference to aforementioned content about Pd-containing plating solution of the present invention.
In the step of the palladium plating of the inventive method or palladium alloy membrane, can use the electroplate liquid that contains single palladium salt or two kinds or multiple palladium salt to reach to carry out the one or many electroplating processes.In addition, also can repeatedly use the electroplate liquid that contains identical or different palladium salt to carry out in the electroplating processes in this.For example, can be earlier be that the electroplate liquid of palladium salt carries out first electroplating processes with the sulfur acid palladium, plating skim palladium film on carrier is that the electroplate liquid of palladium salt carries out a follow-up plating and handles to contain Palladous chloride then, so that the film of the palladium with desired total thickness to be provided again.In this,,, can save the cost of palladium plating or palladium alloy membrane so provide desired plated film with aforementioned two stage manner because the price of Palladous chloride is comparatively cheap.In this, also can be earlier be that the electroplate liquid of palladium salt carries out first electroplating processes to contain Palladous chloride, be that the electroplate liquid of palladium salt carries out follow-up plating and handles with the sulfur acid palladium again.In addition, can any suitable mode carry out this second plating processing, as electrochemical plating, wireless plating technology, vacuum splashing and plating method or cold-rolling practice etc.
In the process of palladium plating or palladium alloy membrane, palladium ion is accepted electronics formation metallic palladium and is deposited on the carrier in the negative electrode place, negative electrode also has hydrogen simultaneously and produces, and this will cause hydrogen and palladium common deposited on carrier, cause gained to contain palladium coating and be easy to generate embrittlement.For avoiding aforementioned, can in palladium or palldium alloy electroplating process, produce flow-disturbing, to reduce or to avoid the interference of hydrogen at electroplate liquid because of the embrittlement phenomenon due to the hydrogen.Can adopt any suitable means to produce this flow-disturbing, for example (but not as limit) can rotate the porous metal carrier as described above, and/or reaches required flow-disturbing by stirring operations such as current stirring, pneumatic blending, negative electrode stirring or ultrasound stirrings.In this, through finding, when adopting the mode of rotating the porous metal carrier when producing flow-disturbing, under same current density condition, the rotating speed of carrier is high more, and the quality of gained palladium or palldium alloy electrolytic coating is good more, and promptly the crystalline network of rete is fine and close more.According to the present invention, the rotating speed of this metallic carrier generally is not to be higher than 1000rpm, is preferably to be controlled in 100rpm to the 500rpm scope.
In the inventive method, can before electroplating, carry out some pre-process to this porous metal carrier earlier, for example degreasing, welding and leveling.Specifically, the porous metal carrier of being buied on the market at present nearly all speckles with greasy dirt on the surface, and this will isolate electroplate liquid and carrier and influence galvanized effect, makes gained coating so bubbling, peeling occur or phenomenon such as peel off.For exempting this phenomenon, generally can utilize organic solvent (for example toluene or acetone) to clean the inside and outside greasy dirt of porous metal carrier, carry out skimming treatment.After skimming treatment, can optionally grind this porous metal carrier in the mechanicalness mode, for example utilize sand paper No. 600, the zone of oxidation that is produced when work hardening layer that is produced during because of the powder metallurgy program when preparing and sintering to remove this metallic carrier.
In addition, can be before the step of carrying out palladium plating of the present invention or palladium alloy membrane, first plating one medium layer is on this porous metal carrier.Specifically, use medium layer on the one hand the hole of porous metal carrier is dwindled, promptly fill hole and form smooth carrier surface gradually, be beneficial to and obtain good palladium or the palladium alloy membrane of density; On the other hand, medium layer can improve the sticking power between palladium or palladium alloy membrane and porous metal carrier, the phenomenon that prevention is peeled off, the work-ing life of prolongation palladium or palladium alloy membrane.For example (but not this to exceed), the material that can be selected from following group is to provide this medium layer: nickel, copper, silver, gold, platinum and combination thereof, this medium layer is preferably by nickel to be formed.In this, also can repeat secondary or medium layer plating step repeatedly, and can in electroplating process, produce flow-disturbing at electroplate liquid according to situation, disturb the galvanizing process of medium layer to avoid formed hydrogen.Use about the medium layer technology, be published in Journal of Catalysis, 170,1997, p.181, Renouprez, the articles that the people showed such as 1 J.F., be published in Journal of Membrane Science, 153,1999, the article that the people showed such as Seung-Eun Nam p.163, be published in Journal of Membrane Science, 170,2000, p.91 the article that the people showed such as Seung-Eun Nam, and be published in Journal of MembraneScience, 192,2001, p.177Seung-Eun the article that the people showed such as Nam discloses all to some extent, and the full text content of these articles is incorporated by reference herein.
Forming medium layer with nickel is example, and a kind of enforcement aspect that can be used for medium layer galvanizing process of the present invention is described.In this, the porous metal carrier is inserted in the coating bath of nickel preplating through after the pre-treatment; Wherein, plating bath temperature is that 30 degree Celsius are to 50 degree; Carrier speed is 500rpm; Electric current is 5A/dm
2To 10A/dm
2, be preferably 7A/dm
2To 10A/dm
2About 3 minutes to 6 minutes of electroplating time is preferably 4 minutes to 5 minutes.Afterwards, washing (for example ultrasound washing) this porous metal carrier through nickel preplating is inserted it and is carried out nickel plating second time program in the nickel bath; Wherein, plating bath temperature is that 30 degree Celsius are to 50 degree; Carrier speed is 500rpm; Electric current is 2A/dm
2To 6A/dm
2, be preferably 4A/dm
2To 6A/dm
2Electroplating time is about 3 minutes to 7 minutes, is preferably 5 minutes to 7 minutes.Afterwards, through water-washing step repeatedly, oven dry promptly obtains the porous metal carrier of plating medium layer again.
When electro-plating method of the present invention being applied to, can after skimming treatment, optionally utilize as the two ends of suitable modes such as argon welding to engage with other metal tube fittings of purifier apparatus with this porous metal carrier as the providing of the required pipe fitting of hydrogen purification.Again mechanical polishing is as the aforementioned carried out on the surface of this porous metal carrier, the zone of oxidation that work hardening layer that is produced because of the powder metallurgy program when preparing to remove this metallic carrier and sintering process are produced, and remove because of the left vestige of aforementioned welding, guarantee the leveling of porous metal carrier surface, improve follow-up galvanized effect.Then, the porous metal carrier with after the water cleaning leveling can use for follow-up plating.
Fig. 1 shows with the inventive method provides one of a palladium or palladium alloy membrane to implement aspect on the porous metal carrier.As shown in Figure 1, the porous metal carrier is earlier through pre-process steps such as degreasing, pipe fitting welding and surface evenings, after washing and oven dry optionally, again through nickel preplating, washing, nickel plating, washing, and optionally processing such as oven dry, carry out palladium plating, washing at last, reach drying, the metal tube that is combined into by porous metal carrier and palladium film is provided.
Therefore, the present invention provides a complex body that contains palladium or palladium alloy membrane in addition, and it comprises: a porous metal base material; One medium layer is overlying on this substrate surface; And a palladium or a palladium alloy membrane, be overlying on this medium layer; Wherein, when the pressure that this palladium or palladium alloy membrane are higher than this palladium or palladium alloy membrane side in the pressure of this complex body base material side reaches 3 bar absolute pressures, still there is not the phenomenon of peeling off in fact; Be preferably and reach 5 bar absolute pressures, better when reaching 10 bar absolute pressures, still there is not the phenomenon of peeling off in fact.
In complex body of the present invention, this porous metal base material is as described above, but chosen from Fe, iron alloy, copper, copper alloy, nickel, nickelalloy and combination thereof are preferably the use iron alloy, and are the best based on considering to adopt the stainless steel that belongs to iron alloy on the economic benefit.Should the medium layer between between base material and palladium or palladium alloy membrane then can be made up of the material that is selected from following group: nickel, copper, silver, gold, platinum and combination thereof wherein, when being base material with the stainless steel, being preferably and adopting nickel so that this medium layer to be provided.
When utilizing Pd-containing plating solution of the present invention and electrochemical plating to prepare palladium on the porous metal carrier or palladium alloy membrane, compared to electroless plating palladium membrane prepare mode quite consuming time in the past, can shorten about 10 times preparation time, significantly promote preparation speed, and need not heat treatment process.In addition, compared to what known electroless plating method provided, the palladium that electrochemical plating of the present invention provided or the crystal grain of palladium alloy membrane are comparatively careful, and when being applied in the hydrogen purification element, the hydrogen permeability that is provided is prepared not less than electroless plating method.Moreover traditional palladium or palladium alloy membrane have the problem of hydrogen embrittlement, in this, through find that the hydrogen embrittlement phenomenon does not all take place for palladium of the present invention or palladium alloy membrane, has higher applicability under low temperature and high temperature.Relate to phase transformation between palladium and hydrogen about the hydrogen embrittlement problem of traditional palladium or palladium alloy membrane, its correlative detail can be with reference to being published in Int.J.Hydrogen Energy, Vol.21, No.6, pp.461-464,1996, the article that F.A.Lewis showed, be published in Electrochimica Acta., Vol.41, No.6, pp.843-844,1996, the articles that the people showed such as Tea-Hyun Yang, and be published in Progress in Surface Science, Vol.48, Nos.1-4, pp.3-14,1995, the articles that the people showed such as E.Nowicka, these article contents be incorporated herein sentence for reference.
Now with following concrete enforcement aspect further to illustrate the present invention.
Embodiment
Example 1 (palladous sulfate electroplate liquid system)
A. the pre-treatment of porousness stainless steel carrier
With the porousness stainless steel pipe with toluene and acetone clean, after the degreasing, sawing 15 cm lengths and plain metal tubing are set up in automatic rotation welding machine, the argon gas that feeds 8 ml/min utilizes argon welding to be welded into the required carrier of palladium plating film in pipe.Carrier after the welding utilizes No. 600 sand paper to flatten to the porousness stainless steel carrier and with common tubing weld position in the mechanical polishing mode, again through the ultrasound washing, places the drying in oven of 150 degree Celsius after the mechanical polishing.The helium that utilizes 1 bar absolute pressure earlier this moment is by the flow that passes through of test gas outward in the carrier, and its numerical value is about 20 liters/minute.
B. the plating of medium layer
Pre-galvanized carrier part, its exposed area are 50 square centimeters.Treated carrier is inserted (120 centimetres of radiuses, 200 centimetres of height) in the nickel preplating coating bath, and pre-coating bath contains 2 liters plating bath, and plating bath composition and electroplating parameter are as shown in table 1.Wherein, the carrier part of pre-plating nickel, its exposed area are 50 square centimeters.Preplating one nickel dam is after on the carrier, and through the ultrasound washing, the carrier that will have nickel preplating is again inserted (120 centimetres of radiuses, 200 centimetres of height) in the nickel bath, and nickel bath includes 2 liters of plating bath, and plating bath composition and electroplating parameter are as shown in table 2.Through repeatedly washing, place the drying in oven of 150 degree Celsius after, again with the helium of 1 bar absolute pressure by the flow that passes through of test gas outward in the carrier, its numerical value is about 4 liters/minute.
Table 1
Table 2
C. palladium plating film
The carrier of this nickeliferous medium layer of gained is inserted (120 centimetres of radiuses, 200 centimetres of height) in the palladium plating plating bath groove, and groove includes 2 liters of plating bath, and plating bath composition and electroplating parameter are as shown in table 3.Again through repeatedly washing, the product of finishing place 150 ℃ baking oven inner drying after the plating.At last, can on the porousness stainless steel carrier, obtain the palladium film of crystalline network densification.
Table 3
Example 2 (carrier speed test)
Repeat operational condition and the step of A to C in the example 1, but the current density of setting palladium plating is 1A/dm
2, and carry out palladium in the carrier speed of 10rpm, 50rpm, 100rpm, 200rpm and 500rpm and electroplate.Make after the palladium film, utilize sweep electron microscope (SEM) observation post to get the palladium membrane structure.Fig. 2 is the SEM figure that is presented at gained palladium film under the carrier speed of 10rpm (A), 50rpm (B), 100rpm (C), 200rpm (D) and 500rpm (E) respectively, can be found under the same density conditions, and high carrier speed can make fine and close relatively palladium film.
Example 3 (Palladous chloride electroplate liquid system)
Carry out the plating of palladium film with the step that is same as A to C in the example 1, but adopt bath element as shown in table 4 and electroplating parameter.
Table 4
Example 4 (preparation of palladium-copper alloy film)
Carry out the plating of palladium alloy membrane with the step that is same as A to C in the example 1, but adopt bath element as shown in table 5 and electroplating parameter.Make after the palladium alloy membrane, utilize sweep electron microscope (SEM) observation post to get the structure of palladium alloy membrane, as shown in Figure 3A; In addition (Energy DispersiveX-ray spectrometer EDX) carries out the analysis of components of palladium alloy membrane, and the result is shown in Fig. 3 B with the energy dispersion x-ray spectrometer.
Table 5
Example 5 (using different electroplate liquids to electroplate in regular turn)
Repeat the step of A to C in the example 1, on the porous metal carrier, but electroplating time changes 30 minutes into the listed plating bath prescription of table 3 and the condition of plating palladium plating film.Then, take out gained carrier and repeatedly, electroplate this gained carrier with listed plating bath prescription of table 4 and plating condition again with washed with de-ionized water.Make after the palladium film, utilize sweep electron microscope (SEM) observation post to get the structure of palladium film, as shown in Figure 4.
Example 6 (helium permeability test)
Under the room temperature, feed the inboard of the porous metal carrier pipe fitting that contains the palladium film (being designated hereinafter simply as " film pipe ") of example 1 gained with 4 bar absolute pressure helium, and be placed in the water-bath, observe film pipe compactness extent, find helium and can't be via the film pipe by internal penetration to outside, represent that the internal pressure that this film pipe can bear helium is 4 bar absolute pressures.
Example 7 (argon gas permeability test)
Utilize device shown in Figure 5, the film pipe 2 of this example 1 gained is placed a double tube reactor 3.Under the room temperature, feed in the reactor 3 through gas feed mouth 1, and open the outer side outlet 5 of film pipe, make inside reactor be full of argon gas with argon gas.Then close the outer side outlet 5 of obturator canal, make reactor begin back pressure, when treating that pressure arrives 10 bar absolute pressures, side outlet 4 is observed and whether is had argon gas and infiltrate into film pipe inboard via the hole of film pipe in the film pipe, experimental result is found, there is no argon gas autoreactor 3 and infiltrate into film pipe inboard via film pipe 2, expression film pipe 2 is in 10 external pressures that can bear argon gas below the bar absolute pressure safely of external pressure.
Example 8 (hydrogen permeate test)
Similarly, use the device of Fig. 5 and the film pipe 2 of example 1 gained, at room temperature, argon gas is fed in the reactor 3 through gas feed mouth 2, and open the outer side outlet 5 of film pipe, make reactor 3 inside be full of argon gas.Then, reactor 3 is warming up to 380 ℃ by room temperature with 2.5 ℃/minute heat-up rate.Change feed gas into technical grade hydrogen, and wait hydrogen catches up with the remaining argon gas in the reactor 3 from reactor 3, then adjust the relief valve 7 at outer side outlet 5 places of film pipe, make reactor pressure keep 5 bar absolute pressures, this moment, hydrogen can be by the difference of pressure difference, infiltration filmed passing tube 2 side outlet 4 to the film pipe, measuring this moment hydrogen permeate amount is 727 ml/min.Adjust the relief valve 7 at outer side outlet 5 places of film pipe, make the pressure of reactor 3 maintain 10 bar absolute pressures, measuring at this moment, the hydrogen permeate amount is 1481 ml/min.The result shows that the prepared palladium film of the present invention has good hydrogen permeate rate.
Example 9 (hydrogen embrittlement test)
The porousness Stainless Steel tubing that welding is good utilizes No. 600 sand paper to carry out mechanical polishing, then this tubing is inserted in 10 mole hydrochlorides 3 to 5 minutes, again with washed with de-ionized water.Afterwards, gained tubing was dipped in the tin chloride sensitizing solution 5 minutes, be dipped in regular turn again in the deionized water in 2 minutes, Palladous chloride activation solution 5 minutes and deionized water in 2 minutes, repeat above-mentioned steps 10 times.After finishing, activated tubing is dipped in (this plating bath composition comprises ammonium chloride palladium and reductive agent diamine (hydrazine)) in the electroless plating plating bath, to obtain porousness stainless steel pipe (hereinafter referred " electroless plating palladium film pipe fitting ") through the tool palladium film of electroless plating method preparation.
Under room temperature, the pipe fitting of getting this electroless plating palladium film pipe fitting and example of the present invention 1 gained carries out the hydrogen embrittlement experiment.At first, will feed the hydrogen of 3 bar absolute pressures in the electroless plating palladium film pipe fitting, as shown in Figure 6, electroless plating palladium film has produced hydrogen embrittlement, and peeling off phenomenon.Then, all there is not the generation of hydrogen embrittlement phenomenon with feeding the hydrogen of 3 bar absolute pressures, 5 bar absolute pressures and 10 bar absolute pressures in the palladium plating film pipe fitting of the present invention respectively, found that.
Afterwards, service temperature is brought up near the transformation temperature of palladium, promptly between 250 ℃ to 300 ℃; Test feeding 3 bar absolute pressures, individual 5 bar absolute pressures and 10 bar absolute pressures in the palladium plating film pipe fitting of the present invention respectively again.Found that, under this phase change temperature, after 600 hours, the generation gas leakage situation that palladium plating film of the present invention just blows slowly but still do not have and to peel off phenomenon, as shown in Figure 7.
Example 10 (purifying hydrogen test)
This example is to utilize the device of Fig. 5 and the film pipe 2 of example 1 gained to test equally, at first adjust the relief valve 7 at outer side outlet 5 places of film pipe, make reactor 3 pressure keep normal pressure, and be feed gas with the mixed gas that contains 75% hydrogen and 25% carbonic acid gas, with these experimental observation film pipe 2 obtainable hydrogen purities.Continue this mixed gas is fed in the reactor 3, then adjust the relief valve 7 at outer side outlet 5 places of film, make reactor 3 internal pressures be maintained at 5 bar absolute pressures, this moment is by action of pressure, and the hydrogen in the reactor 3 can permeate filmed passing tube 2 side outlet 4 to the film pipe.Through measure finding, this moment film pipe 2 outer to survey the exit end hydrogen flowing quantities be 326 ml/min, hydrogen purity is higher than 99.997% (wherein CO, CO
2And CH
4Concentration all less than 10ppm), outer side outlet 5 flows of film pipe are 465 ml/min, hydrogen content is reduced to 57.5% by 75% in original source gas, is equivalent to 55% hydrogen recovery rate.
Afterwards, adjust the relief valve 7 at outer side outlet 5 places of film pipe again, make reactor 3 internal pressures be maintained at 10 bar absolute pressures, pass through action of pressure this moment, hydrogen in the reactor 3 can penetrate palladium film side outlet 4 to the film pipe, through measure finding that this moment, the permeate end hydrogen flowing quantity was 649 ml/min, hydrogen purity is higher than 99.997% (wherein CO, CO
2And CH
4Concentration all less than 10ppm), outer side outlet 5 flows of film pipe are 794 ml/min, hydrogen content is reduced to 54.6% by original source gas 75%, is equivalent to 60% hydrogen recovery rate.
Example 11
As shown in Figure 8, water vapour recombining reaction device 8 is connected with palladium film pipe reactor 9 (the film pipe that comprises example 1 gained).With 2.5 ℃/centimeter temperature rise rate, water vapour recombining reaction device 8 is risen to 280 ℃ by room temperature, palladium film pipe reactor 9 rises to 350 ℃ by room temperature.During intensification, feed reactor as shielding gas with argon gas.After treating that temperature rises to design temperature, with the mixing liquid of pump 10 charging methyl alcohol and water, reaction generates hydrogen and carbonic acid gas in water vapour recombining reaction device 8 districts to make methyl alcohol and water, and this mixed gas carries out hydrogen purification and separates in palladium film pipe reactor 9 zone purifications of flowing through.Control relief valve 12 makes palladium film pipe reactor 9 internal pressures keep 10 bar absolute pressures.Can get the hydrogen permeate amount this moment is 30 liters/hour, and hydrogen purity is 99.95%.
The above embodiments only are used for illustrating enforcement aspect of the present invention, and explain technical characterictic of the present invention, are not to be used for limiting protection category of the present invention.Any person skilled in the art person can unlabored change or the arrangement of the isotropism scope that all belongs to the present invention and advocated, and the scope of the present invention should be as the criterion with following the application's claim scope.
Claims (40)
1. Pd-containing plating solution, it is to comprise:
Palladous sulfate, content are 2 grams per liter to 200 grams per liters (calculating with palladium);
A kind of active conduction salt, content is 10 grams per liter to 200 grams per liters;
A kind of misfit agent, content are 10 grams per liter to 150 grams per liters; And
A kind of buffer reagent, content are to make the pH value of this electroplate liquid 9 to 12.
2. electroplate liquid according to claim 1 is characterized in that misfit agent that it comprises activity conduction salt of the palladous sulfate of 5 grams per liter to 50 grams per liters (calculating with palladium), 70 grams per liter to 150 grams per liters, 30 grams per liter to 70 grams per liters and content are the pH value that makes this electroplate liquid at 10 to 11 buffer reagent.
3. electroplate liquid according to claim 1 is characterized in that this activity conduction salt is to be selected from the compound that sulfate ion can be provided.
4. electroplate liquid according to claim 1 is characterized in that this activity conduction salt is to be selected from following group: the salt of IA family metal, ammonium salt and combination thereof.
5. electroplate liquid according to claim 1 is characterized in that this activity conduction salt is to be selected from following group: sodium-chlor, Repone K, sodium sulfate, ammonium sulfate, ammonium chloride, Sulfothiorine, ammonium thiosulfate, ammonium citrate and combination thereof.
6. electroplate liquid according to claim 1 is characterized in that this activity conduction salt is to be selected from ammonium sulfate.
7. electroplate liquid according to claim 1 is characterized in that this misfit agent is to be selected from following group: boric acid, phosphoric acid salt, hypophosphite, nitrate, tartrate, Citrate trianion, edetate and combination thereof.
8. electroplate liquid according to claim 1 is characterized in that this misfit agent is to be selected from following group: boric acid, sodium phosphate, sodium hydrogen phosphate, Hypophosporous Acid, 50 hydrogen sodium, SODIUMNITRATE, saltpetre, Seignette salt, Trisodium Citrate, Tripotassium Citrate, ammonium citrate, disodium EDTA (EDTA-Na
2), tetrasodium salt of EDTA (EDTA-Na
4), EDTA Dipotassium salt (EDTA-K
2), ethylenediamine tetraacetic acid (EDTA) tripotassium salt (EDTA-K
3), ethylenediamine tetraacetic acid (EDTA) magnesium salts (EDTA-Mg) and the combination.
9. electroplate liquid according to claim 1 is characterized in that this misfit agent is to be selected from following group: saltpetre, ammonium citrate, disodium EDTA (EDTA-Na
2), tetrasodium salt of EDTA (EDTA-Na
4) and combination.
10. electroplate liquid according to claim 1 is characterized in that this buffer reagent is an oxyhydroxide.
11. electroplate liquid according to claim 1 is characterized in that this buffer reagent is to be selected from following group: sodium hydroxide, potassium hydroxide, ammonium hydroxide and combination thereof.
12. electroplate liquid according to claim 1 is characterized in that this buffer reagent is an ammonium hydroxide.
13. electroplate liquid according to claim 1 is characterized in that it further contains sulfuric acid.
14. electroplate liquid according to claim 13 is characterized in that the vitriolic addition is to make every liter of electroplate liquid contain 0.2 mole to 4 moles sulfuric acid.
15. electroplate liquid according to claim 1 is characterized in that it comprises second metal-salt that differs from palladous sulfate in addition.
16. electroplate liquid according to claim 15 is characterized in that this second metal-salt is to be selected from following group: mantoquita, silver salt, golden salt, nickel salt, platinum salt, indium salt and combination thereof.
17. electroplate liquid according to claim 15 is characterized in that this second metal-salt is a mantoquita, is selected from following group: copper sulfate, cupric chloride and combination thereof.
18. electroplate liquid according to claim 17, the content that it is characterized in that this mantoquita are to make every liter of electroplate liquid contain the copper of 0.2 gram to 100 grams.
19. the method that a palladium or palladium alloy membrane are provided on the porous metal carrier, it comprises:
One porous metal carrier is provided; And
Electroplate a palladium or palladium alloy membrane with a Pd-containing plating solution on this porous metal carrier, this Pd-containing plating solution comprises:
A kind of palladium salt, content are 2 grams per liter to 200 grams per liters (calculating with palladium);
A kind of active conduction salt, content is 10 grams per liter to 200 grams per liters;
A kind of misfit agent, content are 10 grams per liter to 150 grams per liters; And
A kind of buffer reagent, content are to make the pH value of this electroplate liquid 9 to 12.
20. method according to claim 19, the material that it is characterized in that this porous metal carrier are to be selected from following group: iron, iron alloy, copper, copper alloy, nickel, nickelalloy and combination thereof.
21. method according to claim 19, the material that it is characterized in that this porous metal carrier is a stainless steel.
22. method according to claim 19 is characterized in that this plating step is to carry out to the bath temperature of 70 degree in 40 degree Celsius.
23. method according to claim 19 is characterized in that this plating step is in 0.01 A/dm
2To 1.5 A/dm
2Current density under carry out.
24. method according to claim 19 is characterized in that this plating step is in 0.2 A/dm
2To 1.0 A/dm
2Current density under carry out.
25. method according to claim 19 is characterized in that rotating this metallic carrier simultaneously when carrying out this plating step.
26. method according to claim 25, the rotating speed that it is characterized in that this metallic carrier is not to be higher than 1000rpm.
27. method according to claim 25, the rotating speed that it is characterized in that this metallic carrier is 100rpm to 500rpm.
28. method according to claim 19 is characterized in that this palladium salt is to be selected from following group: palladous sulfate, dichloro four ammonium palladiums, ammonium chloride palladium, Palladous chloride and combination thereof.
29. method according to claim 19 is characterized in that before this plating step, prior to plating one medium layer on this metallic carrier.
30. method according to claim 29 is characterized in that this medium layer is made up of the material that is selected from following group: nickel, copper, silver, gold, platinum and combination thereof.
31. method according to claim 29 is characterized in that this medium layer is a nickel dam.
32. method according to claim 19 is characterized in that this plating step is one or two stage plating step.
33. method according to claim 32 is characterized in that it is palladium salt that one of this two stages plating step is to use palladous sulfate, another then uses Palladous chloride to be palladium salt.
34. a complex body that contains palladium or palladium alloy membrane, it comprises:
One porous metal base material;
One medium layer is overlying on this substrate surface; And
One palladium or palladium alloy membrane are overlying on this medium layer,
Wherein, when the pressure that this palladium or palladium alloy membrane are higher than this palladium or palladium alloy membrane side in the pressure of this complex body base material side reaches 3 bar absolute pressures, still there is not the phenomenon of peeling off in fact.
35. complex body according to claim 34, the material that it is characterized in that this porous metal base material are to be selected from following group: iron, iron alloy, copper, copper alloy, nickel, nickelalloy and combination thereof.
36. complex body according to claim 34, the material that it is characterized in that this porous metal base material is a stainless steel.
37. complex body according to claim 34 is characterized in that this medium layer is made up of the material that is selected from following group: nickel, copper, silver, gold, platinum and combination thereof.
38. complex body according to claim 34 is characterized in that this medium layer is made up of nickel.
39. complex body according to claim 34 when it is characterized in that pressure that this palladium or palladium alloy membrane are higher than this palladium or palladium alloy membrane side in the pressure of this complex body base material side reaches 5 bar absolute pressures, does not still have the phenomenon of peeling off in fact.
40. complex body according to claim 34 when it is characterized in that pressure that this palladium or palladium alloy membrane are higher than this palladium or palladium alloy membrane side in the pressure of this complex body base material side reaches 10 bar absolute pressures, does not still have the phenomenon of peeling off in fact.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100971301A CN101285203B (en) | 2007-04-13 | 2007-04-13 | Pd-containing plating solution and uses thereof |
| EP07123143A EP1983076A2 (en) | 2007-04-13 | 2007-12-13 | Palladium-containing plating solution and its uses |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100971301A CN101285203B (en) | 2007-04-13 | 2007-04-13 | Pd-containing plating solution and uses thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101285203A true CN101285203A (en) | 2008-10-15 |
| CN101285203B CN101285203B (en) | 2011-04-20 |
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ID=39544944
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100971301A Expired - Fee Related CN101285203B (en) | 2007-04-13 | 2007-04-13 | Pd-containing plating solution and uses thereof |
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|---|---|
| EP (1) | EP1983076A2 (en) |
| CN (1) | CN101285203B (en) |
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| CN102120150A (en) * | 2010-12-08 | 2011-07-13 | 南京工业大学 | Gear type hydrogen-permeable palladium or palladium alloy film and hydrogen separator |
| CN102168291A (en) * | 2011-03-16 | 2011-08-31 | 上海中子星化工科技有限公司 | Palladium plating solution |
| CN102586830A (en) * | 2011-01-10 | 2012-07-18 | 深圳市奥美特科技有限公司 | Equipment and method for plating gold or plating palladium on surface of metal wire |
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| CN105401182A (en) * | 2015-10-14 | 2016-03-16 | 佛山科学技术学院 | Plating solution formula and electroplating method for electroplating thick palladium on stainless steel |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3282737A (en) * | 1962-08-27 | 1966-11-01 | Electric Storage Battery Co | Electrodes and electrode material |
| US4486274A (en) | 1981-02-27 | 1984-12-04 | At&T Bell Laboratories | Palladium plating prodedure |
| US6152987A (en) | 1997-12-15 | 2000-11-28 | Worcester Polytechnic Institute | Hydrogen gas-extraction module and method of fabrication |
| JP2002119834A (en) | 2000-10-16 | 2002-04-23 | Mitsubishi Kakoki Kaisha Ltd | Method of manufacturing inorganic hydrogen separating membrane |
| JP3396470B2 (en) | 2000-11-21 | 2003-04-14 | 三菱重工業株式会社 | Method for producing Pd-based hydrogen separation membrane |
-
2007
- 2007-04-13 CN CN2007100971301A patent/CN101285203B/en not_active Expired - Fee Related
- 2007-12-13 EP EP07123143A patent/EP1983076A2/en not_active Withdrawn
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1983076A2 (en) | 2008-10-22 |
| CN101285203B (en) | 2011-04-20 |
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