CN109628898A - A kind of porous carrier surface palladium-silver/titanium oxide composite film and preparation method thereof - Google Patents
A kind of porous carrier surface palladium-silver/titanium oxide composite film and preparation method thereof Download PDFInfo
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- CN109628898A CN109628898A CN201811601170.XA CN201811601170A CN109628898A CN 109628898 A CN109628898 A CN 109628898A CN 201811601170 A CN201811601170 A CN 201811601170A CN 109628898 A CN109628898 A CN 109628898A
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- silver
- palladium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
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Abstract
The invention discloses a kind of porous carrier surface palladium-silver/titanium oxide composite films for belonging to inorganic material film technical field and preparation method thereof.Palladium-silver/titanium oxide composite film is carried on porous carrier in the present invention, and the percent by volume of palladium-silver is 30%-99% in palladium-silver/titanium oxide composite film, and silver-colored weight percent is 20%~30% in palladium-silver；Wherein palladium-silver/titanium oxide composite film by sputtering palladium-silver target and the acquisition of titanium oxide ceramics target in porous carrier surface simultaneously.The defects of porous carrier surface palladium-silver/titanium oxide composite film high temperatures provided by the invention are strong, pin-free and cracking.
Description
Technical field
The invention belongs to inorganic material film technical field, in particular to a kind of porous carrier surface palladium-silver/titanium oxide is compound
Film and preparation method thereof.
Background technique
Palladium and its alloy have high hydrogen permselective property, are widely used in being catalyzed film reaction, hydrogen isolation and purification field.
Traditional catalysis film reaction, hydrogen isolation and purification palladium element use the pure palladium tube of cold-drawn, palldium alloy membrane tube, simple process,
Membrane tube is fine and close reliable, but membrane tube thickness is big, at high cost, low efficiency.The porous carrier palladium membrane technology developed at present closes palladium or palladium
Golden film is carried on porous carrier surface, under the premise of guaranteeing device overall mechanical strength, reduces the thickness and cost of palladium film,
The hydrogen permeability of palladium film is improved, commercial application prospect is wide.
The porous carrier of palladium film is generally cellular glass, porous ceramics, porous metals etc..Cellular glass and porous ceramic matrix
Body brittleness is big, and sealed connection reliability is low, and use receives certain restrictions.Porous metals can to avoid glass with ceramics it is easy
Broken problem can realize by welding manner and be tightly connected that reliability is higher.But Lacunaris metal carrier exists and palladium film
High temperature element issue of inter-diffusion, mostly use porous ceramics as elements diffusion stop transition zone.Therefore, palladium film is in use process
The middle thermal expansion matching that there are problems that with ceramic layer.And palladium film is to cause to open under palladium film operating temperature with ceramic thermal expansion mismatch
One of the main reason for splitting, removing.In addition, palladium film is in the operating condition, for a long time at a temperature of 300-450 DEG C, this will
It causes palladium film crystal grain to grow up roughening, and then forms needle pore defect etc. in palladium film layer, palladium film is caused to fail.
Summary of the invention
The purpose of the present invention is to provide a kind of porous carrier surface palladium-silver/titanium oxide composite film and preparation method thereof,
Specific technical solution is as follows:
A kind of porous carrier surface palladium-silver/titanium oxide composite film specifically: the palladium-silver/titanium oxide composite film load
In on porous carrier；The percent by volume of palladium-silver is 30%-99%, the palladium in the palladium-silver/titanium oxide composite film
Silver-colored weight percent is 20%~30% in silver alloy.
Palladium-silver/the titanium oxide composite film with a thickness of 1-20 microns, preferably 3-10 microns.
The porous carrier is the porous metals of surface coated with titanium oxide layer.
The porous metals material is stainless steel, nickel-based alloys, and preferably porous 316 stainless steel, porous nickel chromium triangle aluminium close
Gold.
The titanium oxide layer with a thickness of 10-20 microns.
Palladium-silver/the titanium oxide composite film is prepared using physical vaporous deposition, it is preferred to use magnetron sputtering method preparation,
It is obtained specifically by palladium-silver target and titanium oxide ceramics target is sputtered simultaneously.
The preparation method of the porous carrier surface palladium-silver/titanium oxide composite film the following steps are included:
(1) in porous metals surface coated with titanium oxide layer as transition zone；
(2) palladium-silver target, titanium oxide ceramics target are used, while sputtering palladium in the porous metals surface that step (1) obtains
Silver alloy target and titanium oxide ceramics target, obtain palladium-silver/titanium oxide composite film.
The sputtering sedimentation time is 4-7 hours in the step (2).
The invention has the benefit that
The present invention is compound by carrying out Pd-Ag alloy membrane with titanium oxide ceramics, on the one hand makes titanium oxide ceramics particle dispersion
It is distributed in continuous palladium-silver, pinning effect is played to palladium crystal boundary, increase the difficulty that palladium crystal grain high temperature crystal grain is grown up and is roughened
Degree；On the other hand, the introducing of titanium oxide ceramics can be played the role of adjusting Pd-Ag alloy membrane thermal expansion coefficient, reduce palladium-silver and close
The thermal expansion mismatch of golden film and titanium oxide ceramics transition zone improves the thermal structure stability of palladium film.
Detailed description of the invention
Attached drawing 1 is porous carrier surface palladium-silver/titanium oxide composite film structural schematic diagram provided by the invention；
Label declaration: 1- porous metals；2- porous oxidation ti interlayer；3- palladium-silver/titanium oxide composite film.
Specific embodiment
The present invention provides a kind of porous carrier surface palladium-silver/titanium oxide composite film and preparation method thereof, below with reference to
The present invention is described further for embodiment.
The palladium-silver of porous carrier surface shown in 1/titanium oxide composite film structural schematic diagram with reference to the accompanying drawings, in porous metals 1
Surface coats one layer of titanium oxide and forms porous oxidation ti interlayer 2, and palladium-silver/titanium oxide composite film 3 is carried on porous titanium oxide
On transition zone 2.Porous oxidation ti interlayer 2 stops porous metals 1 and 3 high temperature of palladium-silver/titanium oxide composite film as transition zone
Under element counterdiffusion.
Embodiment 1
The preparation of porous stainless steel surface palladium-silver/titanium oxide composite film, specifically:
Elder generation coats one layer of titanium oxide as transition zone on 3 inches of porous stainless steel disc surfaces, obtains the porous of surface modification
Carrier；Then on surface, modified 3 inches of porous stainless steel on pieces prepare palladium-silver/titanium oxide composite film: being closed using palladium-silver
Golden (silver content 27wt%) target, titanium oxide target, palladium-silver are powered using DC power supply, and titanium oxide is supplied using radio-frequency power supply
Electricity, Ar is as build-up of luminance gas.When back end vacuum is better than 2 × 10-4After Pa, 15 points are cleaned with Ar plasma bombardment in sputtering chamber
Clock.By sputtering palladium-silver target and titanium oxide target simultaneously, palladium-silver/titanium oxide composite film is obtained, sputtering chamber air pressure is
0.85Pa, target-substrate distance 100mm, palladium-silver sputtering power are 50W, and the sputtering power of titanium oxide is 120W, and sedimentation time is 7 small
When.Using scanning electron microscope test, palladium-silver/titanium oxide composite film is with a thickness of 3 microns, palladium-silver/titanium oxide THIN COMPOSITE
Palladium-silver volume content is 35% in film.
It is small that prepared porous stainless steel surface palladium-silver/titanium oxide composite film is placed in heat preservation 72 under 700 DEG C of nitrogen atmospheres
When, laminated film it is pin-free and cracking the defects of, helium leak rate be better than 10-9Pa·m3/s。
Embodiment 2
The preparation of porous stainless steel surface palladium-silver/titanium oxide composite film, specifically:
Elder generation coats one layer of titanium oxide as transition zone on 3 inches of porous stainless steel disc surfaces, obtains the porous of surface modification
Carrier；Then on surface, modified 3 inches of porous stainless steel on pieces prepare palladium-silver/titanium oxide composite film: being closed using palladium-silver
Golden (silver content 27wt%) target, titanium oxide target, palladium-silver are powered using DC power supply, and titanium oxide is supplied using radio-frequency power supply
Electricity, Ar is as build-up of luminance gas.When back end vacuum is better than 2 × 10-4After Pa, 15 points are cleaned with Ar plasma bombardment in sputtering chamber
Clock.By sputtering palladium-silver target and titanium oxide target simultaneously, palladium-silver/titanium oxide composite film is obtained, sputtering chamber air pressure is
0.85Pa, target-substrate distance 100mm, palladium-silver sputtering power are 400W, and the sputtering power of titanium oxide is 120W, and sedimentation time is 4 small
When.Using scanning electron microscope test, palladium-silver/titanium oxide composite film is with a thickness of 8 microns, palladium-silver/titanium oxide THIN COMPOSITE
Palladium-silver volume content is 95% in film.
Prepared porous stainless steel surface palladium-silver/titanium oxide composite film is kept the temperature 72 hours under 700 DEG C of nitrogen atmospheres,
The defects of laminated film is pin-free and cracks, helium leak rate is better than 10-9Pa·m3/s。
Embodiment 3
The preparation of porous nichrome aluminum alloy surface palladium-silver/titanium oxide composite film, specifically:
Elder generation coats one layer of titanium oxide as transition zone in 3 inches of porous nickel chromium triangle aluminum flake surfaces, obtains the porous of surface modification
Carrier；Then palladium-silver/titanium oxide composite film is prepared on the porous nickel chromium triangle aluminium flake in modified 3 inches of surface: being closed using palladium-silver
Golden (silver content 23wt%) target, titanium oxide target, palladium-silver are powered using DC power supply, and titanium oxide is supplied using radio-frequency power supply
Electricity, Ar is as build-up of luminance gas.When back end vacuum is better than 2 × 10-4After Pa, 15 points are cleaned with Ar plasma bombardment in sputtering chamber
Clock.By sputtering palladium-silver target and titanium oxide target simultaneously, palladium-silver/titanium oxide composite film is obtained, sputtering chamber air pressure is
0.85Pa, target-substrate distance 100mm, palladium-silver sputtering power are 100W, and the sputtering power of titanium oxide is 250W, and sedimentation time is 5 small
When.Using scanning electron microscope test, palladium-silver/titanium oxide composite film is with a thickness of 3 microns, palladium-silver/titanium oxide THIN COMPOSITE
Palladium-silver volume content is 85% in film.
Prepared porous nickel chromium triangle aluminium surface palladium-silver/titanium oxide composite film is kept the temperature 72 hours under 600 DEG C of nitrogen atmospheres,
The defects of laminated film is pin-free and cracks, helium leak rate is better than 10-9Pa·m3/s。
Claims (10)
1. a kind of porous carrier surface palladium-silver/titanium oxide composite film, which is characterized in that the palladium-silver/titanium oxide composite film
It is carried on porous carrier；The percent by volume of palladium-silver is 30%-99%, institute in the palladium-silver/titanium oxide composite film
Stating weight percent silver-colored in palladium-silver is 20%~30%.
2. porous carrier surface palladium-silver/titanium oxide composite film according to claim 1, which is characterized in that the palladium-silver/
Titanium oxide composite film with a thickness of 1-20 microns.
3. porous carrier surface palladium-silver/titanium oxide composite film according to claim 1, which is characterized in that the palladium-silver/
Titanium oxide composite film with a thickness of 3-10 microns.
4. porous carrier surface palladium-silver/titanium oxide composite film according to claim 1, which is characterized in that described porous
Carrier is the porous metals of surface coated with titanium oxide layer.
5. porous carrier surface palladium-silver/titanium oxide composite film according to claim 4, which is characterized in that described porous
Metal material is stainless steel, nickel-based alloys.
6. porous carrier surface palladium-silver/titanium oxide composite film according to claim 4, which is characterized in that the oxidation
Titanium layer with a thickness of 10-20 microns.
7. porous carrier surface palladium-silver/titanium oxide composite film according to claim 1, which is characterized in that the palladium-silver/
Titanium oxide composite film is prepared using physical vaporous deposition.
8. porous carrier surface palladium-silver/titanium oxide composite film according to claim 1, which is characterized in that the palladium-silver/
Titanium oxide composite film passes through while sputtering palladium-silver target and titanium oxide ceramics target obtains.
9. the preparation method of any one of the claim 1~8 porous carrier surface palladium-silver/titanium oxide composite film, feature
It is, comprising the following steps:
(1) in porous metals surface coated with titanium oxide layer as transition zone；
(2) palladium-silver target, titanium oxide ceramics target are used, while being closed in the porous metals surface that step (1) obtains sputtering palladium-silver
Gold target and titanium oxide ceramics target, obtain palladium-silver/titanium oxide composite film.
10. preparation method according to claim 9, which is characterized in that the sputtering sedimentation time is 4-7 in the step (2)
Hour.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776601A (en) * | 1996-10-28 | 1998-07-07 | General Motors Corporation | Titania exhaust gas oxygen sensor |
| CN101216448A (en) * | 2008-01-09 | 2008-07-09 | 浙江大学 | Hydrogen sensor based on Pd-silver filament electrode |
| CN101670245A (en) * | 2008-09-10 | 2010-03-17 | 徐恒泳 | Method for preparing high hydrogen permeation selectivity metal palladium-based composite membrane |
| JP2010119921A (en) * | 2008-11-17 | 2010-06-03 | Ngk Insulators Ltd | Hydrogen separating body and method of manufacturing the same |
| CN101983757A (en) * | 2010-12-06 | 2011-03-09 | 西北有色金属研究院 | Palladium composite membrane taking multihole FeAlCr as substrate and preparation method thereof |
| CN102211043A (en) * | 2011-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | Preparation method of palladium-silver bimetallic catalyst |
-
2018
- 2018-12-26 CN CN201811601170.XA patent/CN109628898A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776601A (en) * | 1996-10-28 | 1998-07-07 | General Motors Corporation | Titania exhaust gas oxygen sensor |
| CN101216448A (en) * | 2008-01-09 | 2008-07-09 | 浙江大学 | Hydrogen sensor based on Pd-silver filament electrode |
| CN101670245A (en) * | 2008-09-10 | 2010-03-17 | 徐恒泳 | Method for preparing high hydrogen permeation selectivity metal palladium-based composite membrane |
| JP2010119921A (en) * | 2008-11-17 | 2010-06-03 | Ngk Insulators Ltd | Hydrogen separating body and method of manufacturing the same |
| CN101983757A (en) * | 2010-12-06 | 2011-03-09 | 西北有色金属研究院 | Palladium composite membrane taking multihole FeAlCr as substrate and preparation method thereof |
| CN102211043A (en) * | 2011-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | Preparation method of palladium-silver bimetallic catalyst |
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