CN1198003C - Electrochemical catalyst electrode resulting in high endurance of the combination between coating and metal base - Google Patents
Electrochemical catalyst electrode resulting in high endurance of the combination between coating and metal base Download PDFInfo
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- CN1198003C CN1198003C CN 02106537 CN02106537A CN1198003C CN 1198003 C CN1198003 C CN 1198003C CN 02106537 CN02106537 CN 02106537 CN 02106537 A CN02106537 A CN 02106537A CN 1198003 C CN1198003 C CN 1198003C
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Abstract
The present invention provides an electrochemical catalyst electrode resulting in the high endurance of the combination between a strengthening coating and a metal base plate. High temperature treatment and etching treatment are implemented to the metal base plate of the electrochemical catalyst electrode, and large amounts of corroded holes can be generated on a crystal surface, and the surface of the metal base plate is converted into a metal oxygenized film in an oxygen leading and heating mode. Meanwhile, substrate metal hydride on the surface is removed. An inner coating can penetrate into the holes to form an included angle when being stacked. The metal oxygenized film can prompt and increase the attachment between the inner coating and the base plate and can decrease interface stripping. Meanwhile, an outer coating added with stability elements is formed on the coating for enhancing the stability of the outer surface of the coating. Thus, precious metal liquation can be decreased, the stability can be greatly prolonged, and the service life of the electrochemical catalyst electrode can be greatly increased.
Description
Technical field
The present invention is a kind of electrochemical catalyst electrode that combines weather resistance between coating and metal substrate of strengthening, and can be applicable to and electrolysis or electroplate relevant industry.
Background technology
The electrochemical catalyst pole plate has reaction efficiency height and the low electrochemical properties of voltage, is used in electrolysis or plating industry, and as electrolytic copper foil processing procedure and sewage disposal etc., the benefit that is produced comprises the raising production capacity, saves the energy and reduces environmental pollution.The electrochemical catalyst pole plate can overlay on the metal substrate by precious metal, reversible redox response characteristic by precious metal and transition metal, come the catalyticing anode reaction, and general electrochemical catalyst substrate is because oxide compound coating and substrate interface are easy to generate peeling off passivation, and influence work-ing life of this electrochemical catalyst substrate, think consumption and the mass-produced consideration of saving precious metal in the electrochemical catalyst pole plate, the quality of pole plate and weather resistance are just quite important.In the general electrochemical catalyst pole plate correlation technique, in the processing of metal substrate, be to dig out said minuscule hole by the etching metal substrate surface to amass to increase its attaching surface, patent such as US5672394 and US60715705 as is well known, but the pit that this crystal boundary etching (intergranular etching) technology can produce only appears between crystal and crystalline interface mostly, can't provide a large amount of pits significantly to improve the quantity of pit and the surface-area that metal substrate adheres to.
Summary of the invention
Main purpose of the present invention, be to solve above-mentioned defective, avoid the existence of above-mentioned defective, for realizing above-mentioned purpose, the invention provides a kind of electrochemical catalyst electrode that combines weather resistance between coating and metal substrate of strengthening, utilize a phase transformation and oxide treatment and etch processes and oxide treatment, can on the whole crystal face of metallic substrate surfaces crystal grain, produce a large amount of holes, increase the bond area of substrate and improve coating oxide compound and intermetallic compatibility and bonding force, therefore can avoid interface to produce and peel off; Also can in outer covering layer, suppress the precious metal dissolved to prolong the life-span of assembly in addition by adding stable element.
For realizing above-mentioned purpose, the invention provides a kind of electrochemical catalyst electrode that combines weather resistance between coating and metal substrate of strengthening, utilize this metallic substrate surfaces of a phase transformation and oxidation, make this metal substrate and zone of oxidation interface crystal grain grow precipitate and sensitization; One blast cleaning surface oxide layer exposes the sensitization interface; One etch processes makes with the acid solution etching in metal substrate sensitization surface and produces a large amount of holes on the crystal grain crystal face of this substrate surface, the surface-area that adheres to so as to increase; One contains the oxygen heat treated, and this metallic substrate surfaces is removed the metastable metal hydride on surface, and made its surface change into a metal oxide film simultaneously after etch processes with type of heating under oxygenated environment; Pile up processing with a coating more at last, form an internal coated layer and outer covering layer in regular turn on this metal oxide film, and on outer covering layer, add some stabile elements, can increase the work-ing life of assembly.
Description of drawings
Fig. 1 is Ti metallographic phase conversion characteristic of the present invention and oxidation characteristic reaction descriptions figure.
Fig. 1-1 is the X partial enlarged drawing among Fig. 1.
Fig. 2 is a Ti substrate of the present invention cross section zone of oxidation structure iron.
Fig. 3-1 is distributed in sem observation photo on the metallic substrate surfaces crystal face for precipitate of the present invention.
Fig. 3-2 is the sem observation photo of pit void distribution on the metallic substrate surfaces crystal face of the present invention.
Fig. 3-3 is the sem observation photo in porous metal substrate of the present invention cross section.
Fig. 4-1 is distributed in the sem observation photo of metallic substrate surfaces crystal boundary for precipitate of the present invention.
Fig. 4-2 is the sem observation photo of void distribution of the present invention in metallic substrate surfaces crystal face and crystal boundary.
Fig. 5 is an oxide stack structure iron of the present invention.
Fig. 6 is the durability test figure of electrochemical catalyst electrode of the present invention.
Fig. 7-1 for the present invention in do not have strengthening peeling off the damaged form of doing sth. in advance deterioration because of coating and the generation of substrate interface in conjunction with handling pole plate.
Fig. 7-2 handles pole plate because of the damaged form of the low slowly deterioration of coating dissolved speed for the present invention in strengthening combination.
Label in the accompanying drawing:
Metal substrate ... ... ... ... ... ... ... ..1
Metal oxide film ... ... ... ... ... ... ... 2
Internal coated layer ... ... ... ... ... ... ... ... .3
Outer covering layer ... ... ... ... ... ... ... ... .4
Embodiment
The invention provides a kind of electrochemical catalyst electrode that combines weather resistance between coating and metal substrate of strengthening, utilize precious metal (Ru, Pt, Ir etc.) to keep integrally combining by compatibility high multilevel oxide form coating and high area metal substrate 1, its processing procedure is to form a metal oxide film 2, internal coated layer 3 and outer covering layer 4 on the metal substrate 1 of a porous surface in regular turn, utilize this metal substrate 1 surface of a phase transformation and oxidation, make this metal substrate 1 grow precipitate and sensitization with zone of oxidation interface crystal grain; One blast cleaning surface oxide layer exposes the sensitization interface; One etch processes makes with the acid solution etching in metal substrate 1 sensitization surface and produces a large amount of holes on the crystal grain crystal face of this substrate surface; One contains the oxygen heat treated, with type of heating the metallic surface is changed into a metal oxide film 2 under oxygenated environment; And a coating piles up processing, forms an internal coated layer 3 and outer covering layer 4 in regular turn on this metal oxide film 2, being described as follows of its each step:
(A) high temperature phase transformation and oxide treatment
At first, provide a metal substrate 1, this metal substrate 1 can be Ti, Ta, Zr or its alloy, and this metal substrate 1 is made a porousness handle its treatment step following (is example with pure Ti metal substrate):
(a) the Ti substrate is in oxygenated environment, and with the heat more than 900 ℃ 1 hour (or more than 1 hour), the Ti on the substrate remains in the β phase at this moment in High Temperature Furnaces Heating Apparatus.
(b) keep the High Temperature Furnaces Heating Apparatus temperature to be lower than 900 ℃ and kept 1 hour, the Ti on this moment substrate remains in the α phase.
(c) High Temperature Furnaces Heating Apparatus cooling back is with the zone of oxidation of blast cleaning substrate surface.
Behind above-mentioned treatment step, make on metal substrate 1 surface microstructure and be precipitate and sensitization, referring to Fig. 1, be Ti metallographic phase conversion characteristic of the present invention and oxidation characteristic reaction descriptions figure, Fig. 1 is Ti metal β and the temperature variation of α phase transformation and oxidation relation, X zone among the figure is pure Ti metal and zone of oxidation interface, can know shown in Fig. 1-1 that the temperature of finding out pure Ti metal β and α phase transformation is greatly about 882 ℃; Its Ti metal substrate 1 is Ti substrate of the present invention cross section zone of oxidation structure iron as shown in Figure 2.Metal substrate 1 is by the characteristic of high temperature phase transformation and oxidation, impel this metal substrate 1 and zone of oxidation interface crystal grain to grow precipitate and the situation of sensitization shown in Fig. 3-1, for precipitate of the present invention is distributed in sem observation photo (SEM) on the metal substrate 1 surperficial crystal face.
(B) etch processes
Zone of oxidation with the blast cleaning substrate surface, after exposing the sensitization interface, utilize again an etching mode in metal substrate 1 sensitization surface with the acid solution etching (with 60 ℃ 6M HCl, continue more than 1 hour), make and produce a large amount of pits on the crystal face on whole metal substrate 1 surface, its situation is shown in Fig. 3-2, SEM figure for pit void distribution on the metal substrate 1 surperficial crystal face of the present invention, so can increase the surface-area that coating adheres to, coating is filled in substrate pores to form the angle of tool fixed action simultaneously, by Fig. 3-3 (the SEM figure in porous metal substrate of the present invention cross section), can know has many micro pores on the side surface of seeing metal substrate 1; Wherein this metal substrate 1 is after a phase transformation high temperature oxidation process and etch processes, and metal substrate 1 surperficial crystal face void density can reach more than 20 in every square centimeter, and the hole width is between 30 μ m～100 μ m, and the hole degree of depth is between 30 μ m～100 μ m.
Fig. 4 is for the high temperature oxidation after without phase transformation of metal substrate relatively, with the zone of oxidation of blast cleaning substrate surface, expose the sensitization interface after, utilize again an etching mode in metal substrate 1 surface with the etched situation of acid solution; Fig. 4-1 is the SEM figure that the precipitate that produced is distributed in metallic substrate surfaces crystal face and crystal boundary, and Fig. 4-2 be that void distribution of the present invention is schemed in the SEM of metallic substrate surfaces crystal face and crystal boundary, and pit void density, the degree of depth and width are all relatively low as can be seen.
(C) contain oxygen heat treated and coating and pile up processing
When metal substrate 1 surface after etch processes, under oxygenated environment, remove the metastable metal hydride on surface with type of heating, and the metallic surface changed into a metal oxide film 2, wherein, contain the precious metal coating and can be easier to for making in conjunction with this metal substrate 1, so in internal coated layer 3, contain one with the element of metal substrate 1 compatibility, and combine with the precious metal oxidation with oxidation state, for suppressing coating outside surface precious metal dissolved to electrolytic solution, on coating, form one again and add the outer covering layer 4 of stabilizing element, be illustrated in figure 5 as oxide stack structure iron of the present invention, on metal substrate 1, form a metal oxide film 2 in regular turn, internal coated layer 3 and outer covering layer 4, and coating piles up and can utilize thermolysis, chemical vapor deposition (CVD), sol-gel program (sol-gel process) or plasma spraying oxidation modes such as (plasma spray oxide) forms an internal coated layer 3 and outer covering layer 4 in regular turn on this metal oxide film 2; This internal coated layer 3 comprise at least can with the metal of metal oxide film 2 compatibilities (Ti, Ta, Zr) and a platinum metals (Pt, Ir, Ru, Pd, Os, Rh), and this outer covering layer 4 comprises a platinum metals (Pt, Ir, Ru, Pd at least, Os, Rh) and an admixture, this admixture can be selected from Ti, Ta, Zr, Sb, Nb, Sn adds these admixtures (stable element) and can suppress the precious metal dissolved to prolong the life-span of assembly in outer covering layer 4.
1 electrochemical catalyst electrode that combines weather resistance of above-mentioned reinforcement coating of forming and metal substrate, not only the compatibility of each interlayer improves, interface produces to be peeled off and the influence of passivation also significantly reduces, and prolong the life-span of using, referring to the durability test figure of Fig. 6 for electrochemical catalyst electrode of the present invention, can see that in Fig. 6 sample A handles and the stable of the present invention sample of element in coating of interpolation through the phase transformation of alpha-beta high temperature, its duration of service is about 6500 hours; Sample B has to add stable element, but without alpha-beta phase transformation process (only through high temperature α phase), the time of its use is between 2000～3000 hours; SampleC handles without phase transformation also not add stable element in coating, and its duration of service is only within 1000 hours.So stabilize the time that element all can significantly improve its use through adding in high temperature phase transformation processing and the coating, prolong assembly life-span.
Fig. 7-1 is respectively the present invention and handles pole plate and peel off the damaged form of do sth. in advance deterioration because of coating and substrate interface produce and combine the processing pole plate because of the low slow deterioration breakage form of coating dissolved speed with the present invention in reinforcement in do not have strengthening combine with Fig. 7-2, two figure strengthen as can be known in conjunction with handling thus, have the effect that prevents that coating from peeling off, can significantly prolong assembly life-span.
Claims (10)
1. one kind prepares and utilize to strengthen the method that combines the electrochemical catalyst electrode of weather resistance between coating and metal substrate, metal oxide film (2), internal coated layer (3) and outer covering layer (4) that described electrochemical catalyst electrode comprises a porous surface metal substrate (1), forms in regular turn on described metal substrate, described method comprises:
One metal substrate (1) is provided;
One high temperature phase transformation is handled, utilize a high temperature phase transformation and this metal substrate of oxidation (1) surface, make this metal substrate (1) surface grow precipitate in crystal face and sensitization, wherein said high temperature phase transformation is handled and be may further comprise the steps: earlier this metal substrate is heated being higher than under the phase transformation temperature in oxygenated environment, temperature is remained below under the phase transformation temperature again, remove the zone of oxidation of this metallic substrate surfaces then;
One etch processes makes a large amount of holes of generation on the surperficial crystal grain crystal face of this metal substrate (1) with the acid solution etching in metal substrate (1) surface;
One contains the oxygen heat treated, with type of heating, removes the metastable metal hydride on surface under oxygenated environment, simultaneously metallic surface (1) is changed into a metal oxide film (2); And
One coating piles up processing, can utilize the mode of thermolysis, chemical Vapor deposition process, sol-gel program or plasma spraying oxidation to form an internal coated layer (3) and outer covering layer (4) in regular turn on this metal oxide film (2).
2. method according to claim 1, wherein this metal substrate (1) can be Ti, Ta, Zr or its alloy.
3. method according to claim 1, wherein this metal substrate (1) is after a pyroprocessing and etch processes, the surperficial crystal face void density of metal substrate (1) can reach more than 20 in every square centimeter, and the hole width is between 30 μ m～100 μ m, and the hole degree of depth is between 30 μ m～100 μ m.
4. method according to claim 1, wherein this internal coated layer (3) comprise at least can be compatible with metal oxide film (2) a metal and a platinum metals.
5. method according to claim 1, wherein this outer covering layer (4) comprises a platinum metals and an admixture at least, this admixture can be selected from Ti, Ta, Zr,, Sb, Nb, Sn.
6. according to claim 4 or 5 described methods, wherein this platinum metals comprises Pt, Ir, Ru, Pd, Os, Rh.
7. method according to claim 1, the substrate metal during wherein this high temperature phase transformation is handled is to change mutually and between the α phase at β.
8. one kind is utilized and strengthens the electrochemical catalyst electrode that combines weather resistance between coating and metal substrate, it is characterized in that comprising:
One porous surface metal substrate (1), the surperficial crystal face void density of described metal substrate (1) are every square centimeter more than 20, and the hole width is between 30 μ m～100 μ m, and the hole degree of depth is between 30 μ m～100 μ m;
The metal oxide film (2) that on described metal substrate, forms in regular turn, internal coated layer (3) and outer covering layer (4).
9. electrochemical catalyst electrode according to claim 8, wherein this internal coated layer (3) comprise can be compatible with metal oxide film (2) a metal and a platinum metals.
10. electrochemical catalyst electrode according to claim 8, wherein this outer covering layer (4) comprises a platinum metals and an admixture at least, this admixture can be selected from Ti, Ta, Zr,, Sb, Nb, Sn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02106537 CN1198003C (en) | 2002-02-27 | 2002-02-27 | Electrochemical catalyst electrode resulting in high endurance of the combination between coating and metal base |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02106537 CN1198003C (en) | 2002-02-27 | 2002-02-27 | Electrochemical catalyst electrode resulting in high endurance of the combination between coating and metal base |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1441088A CN1441088A (en) | 2003-09-10 |
| CN1198003C true CN1198003C (en) | 2005-04-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02106537 Expired - Lifetime CN1198003C (en) | 2002-02-27 | 2002-02-27 | Electrochemical catalyst electrode resulting in high endurance of the combination between coating and metal base |
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| Country | Link |
|---|---|
| CN (1) | CN1198003C (en) |
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- 2002-02-27 CN CN 02106537 patent/CN1198003C/en not_active Expired - Lifetime
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| CN1441088A (en) | 2003-09-10 |
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Granted publication date: 20050420 |