CN109136893A - A kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method - Google Patents
A kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method Download PDFInfo
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- CN109136893A CN109136893A CN201811098585.XA CN201811098585A CN109136893A CN 109136893 A CN109136893 A CN 109136893A CN 201811098585 A CN201811098585 A CN 201811098585A CN 109136893 A CN109136893 A CN 109136893A
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1806—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by mechanical pretreatment, e.g. grinding, sanding
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Methods, first niobium foil is pre-processed using mechanical rubbing method, remove the oxide layer of its outer surface, then niobium foil is immersed into plating palladium liquid under conditions of 30-80 DEG C, palladium-niobium-palladium-based composite membrane is obtained after plating 15-60 minutes.The pretreatment is the following steps are included: carry out outer surface polishing and planarizing process to niobium foil using SiC sand paper, then be cleaned by ultrasonic 5-10min with deionized water；Then it is immersed into hydrofluoric acid, is taken out after ultrasonic 5-10min, then immerse in deionized water, taken out after being cleaned by ultrasonic 5-10min.The preparation method is ingenious in design, easy to operate, at low cost, environmental-friendly, and palladium-niobium obtained-palladium-based composite membrane surface layer is fine and close, and defect is few, thus hydrogen permeability energy with higher.
Description
Technical field
The present invention relates to compound field of membrane preparation, and in particular to a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method.
Background technique
In the deuterium tritium fuel circulating treatment procedure of fusion reactor and hydrogen manufacturing that hydrogen energy source utilizes, hydrogen storage process
In, it is related to the technique that a large amount of hydrogen and its isotope are isolated and purified from other gases.The separation of hydrogen has pressure-variable adsorption
Method (PSA), temp.-change adsorptive process (TSA), Deep Cooling Method and embrane method etc., wherein embrane method due to small investment, low energy consumption, it is high-efficient,
The advantages that easy to operate, has become the hot spot of research.The membrane material that can be used for hydrogen separation has polymeric membrane, Metal Palladium and its alloy
Film, molecular screen membrane, carbon film and silicon dioxide film etc., wherein palladium and its alloy film are because having many advantages, such as that hydrogen permeability is strong, selectivity is high
And it is concerned.However, to constrain it extensive in common hydrogen isotope separation purifying process for the high price of precious metal palladium
Using.It is compared with palladium, refractory metal niobium can achieve higher infiltration hydrogen rate, and its good mechanical property at appropriate temperatures, easily
In machine-shaping, cost is only 1/the tens of palladium, is a kind of very promising hydrogen separation membrane material.Metal niobium is made
It is inhibition of its surface film oxide to hydrogen to seep hydrogen membrane material to need the major issue solved.Experiment shows vacuum
Annealing and ion sputtering can effectively remove surface film oxide.If after removing surface film oxide, then plating one layer of palladium film,
The Penetration Signature that can then make full use of it high to hydrogen atom.The preparation method of palladium film reported at present mainly has chemical plating
Method, galvanoplastic, chemical vapour deposition technique, physical vaporous deposition, magnetron sputtering method, plasma spraying method, photocatalytic method etc., and
Electroless plating method is acknowledged as best palladium membrane preparation method.
The chemical pd-plating process reported in contemporary literature and patent is all more complicated, it is necessary to pass through cumbersome sensitization and activation
Step just can be carried out, and need longer plating time.Reducing agent in plating solution is mostly used toxic hydrazine or hydrazine derivative, and
And with the consumption of hydrazine in aqueduct, plating rate sharply declines.And since reserve is high and cause very high in palladium coating for hydrogen
Internal stress is also easy to produce crackle when thick, will cause instantaneous crackle and delamination when sample is removed plating solution.Therefore how by simple
It operates, avoid preparing the emphasis that fine and close, uniform, palladium-based composite membrane that is not cracking is research using toxic reagent, it is multiple for palladium
Close the industrialization important in inhibiting of film.
Summary of the invention
The purpose of the present invention is to solve above-mentioned technical problems, and it is standby to provide a kind of palladium-niobium-palladium-based composite membrane chemically plating
Method, the preparation method is ingenious in design, easy to operate, at low cost, environmental-friendly, and palladium-niobium obtained-palladium-based composite membrane surface layer causes
Close, defect is few, thus hydrogen permeability energy with higher.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method first locates niobium foil using mechanical rubbing method in advance
Reason, removes the oxide layer of its outer surface, then niobium foil is immersed into plating palladium liquid under conditions of 30-80 DEG C, plating 15-60 points
Palladium-niobium-palladium-based composite membrane is obtained after clock.
Specifically, the pretreatment is the following steps are included: carry out outer surface polishing to niobium foil using SiC sand paper, to go
Planarizing process is carried out except surface oxide layer and to plating matrix, to improve the adhesive force of coating, then it is clear with deionized water ultrasound
Wash 5-10min；Then it is immersed into hydrofluoric acid, is taken out after ultrasonic 5-10min, sufficiently remove removing oxide layer, activate table to be plated
Face is finally immersed in deionized water again, is taken out after being cleaned by ultrasonic 5-10min.
It specifically, is successively to use 280 mesh, 600 mesh, 1000 when carrying out outer surface polishing to niobium foil using SiC sand paper
The SiC sand paper of mesh and 1500 mesh is polished.The polishing time is according to judgement with niobium film surface state: can cover upper one of sand paper
The scratch of generation can change a mesh sand paper.
More specifically, the mass concentration of the hydrofluoric acid is 28%.
Further, the plating palladium liquid is to be mixed by soluble palladium salt, reducing agent, stabilizer and buffer, and add
Enter hydrochloric acid solution and adjusts its pH to 7-10.
Further, the soluble palladium salt in the plating palladium liquid is palladium chloride, and its concentration is 0.3-4g/L.
Further, the reducing agent in the plating palladium liquid is sodium hypophosphite, and its concentration is 2-20g/L.
Further, the stabilizer in the plating palladium liquid is ammonium chloride, and its concentration is 10-50g/L.
Further, the buffer in the plating palladium liquid is the ammonium hydroxide of mass concentration 28%, and ammonium hydroxide is in plating palladium liquid
Concentration be 100-200ml/L.
As a preferred embodiment, the mass concentration of the hydrochloric acid solution is 38%.
Compared with prior art, the invention has the following advantages:
Preparation method of the present invention is ingenious in design, can be prepared using shirtsleeve operation, nontoxic reagent fine and close, uniformly, no
The palladium-based composite membrane cracked, for the industrialization important in inhibiting of palladium-based composite membrane.Its plate before using SiC sand paper to niobium foil into
The two-sided polishing of row, and use hydrofluoric acid clean residual oxide layer；It then, will be pretreated under the conditions of temperature is 30-80 DEG C
Niobium foil immerses chemical plating fluid plating 15-60min, easy to operate, at low cost and environmental-friendly.Especially it plates palladium liquid and contains
Soluble palladium salt (palladium chloride), reducing agent (sodium hypophosphite), stabilizer (ammonium chloride) and buffer (ammonium hydroxide), stabilizer and
Buffer can make in solution that palladium ion concentration is relatively stable, avoid reuniting caused by local palladium ion concentration is excessively high in solution
Phenomenon, the entire palladium liquid that plates have stable pH, stable deposition rate, the water-bath service life of length, excellent water-bath stability, use
It can make coating not generate crack niobium foil chemical plating, keep palladium-niobium obtained-palladium-based composite membrane surface layer fine and close, and defect is few, thus
Hydrogen permeability energy with higher.
Detailed description of the invention
Fig. 1 is the flow chart of preparation method of the present invention.
Fig. 2 is 1000 times of scanning electron microscope diagrams that embodiment 1 obtains sample.
Fig. 3 is 5000 times of scanning electron microscope diagrams that embodiment 1 obtains sample.
Fig. 4 is that embodiment 1 obtains sample plating layer depth composition analysis result figure.
Specific embodiment
The invention will be further described with embodiment for explanation with reference to the accompanying drawing, and mode of the invention includes but not only limits
In following embodiment.
Embodiment 1
A kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method is present embodiments provided, as shown in Figure 1, including following step
It is rapid:
1) it pre-processes: selecting the niobium film of thickness 0.25mm, be cut into 5 × 5mm size；To its it is two-sided successively using 280 mesh,
The SiC sand paper of 600 mesh carries out grinding process, makes its two-sided grinding homogeneity, two-sided smooth, then is cleaned by ultrasonic with deionized water
5min；Then it is immersed into the hydrofluoric acid that mass concentration is 28%, is taken out after ultrasonic 5min, then immerse in deionized water,
It is taken out after ultrasonic cleaning 5min；
2) chemical plating: niobium foil is immersed into plating palladium liquid under conditions of 40 DEG C, palladium-niobium-is obtained after plating 45 minutes
Palladium-based composite membrane；
Wherein, the plating palladium liquid be by palladium chloride, ammonium chloride, sodium hypophosphite and ammonium hydroxide and hydrochloric acid solution configuration and
At pH 7-10.In the plating palladium liquid, palladium chloride (PdCl2) concentration be 0.3g/L, ammonium chloride (NH4Cl) concentration is 10g/
L, sodium hypophosphite (NaH2PO2) concentration be 2g/L, 28% ammonium hydroxide (NH4OH) concentration is 100ml/L, and its hydrochloric acid being added is molten
The mass concentration of liquid is 38% or so, and specific additional amount (additional amount is about 2-6ml/L) and concentration and additional amount can carry out
Subtle adjustment, so that its pH is subject to 7-10.
Embodiment 2
Present embodiments provide a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method, comprising the following steps:
1) it pre-processes: selecting the niobium film of thickness 0.28mm, be cut into 8 × 8mm size；To its it is two-sided successively using 600 mesh,
The SiC sand paper of 1000 mesh and 1500 mesh carries out grinding process, makes its two-sided grinding homogeneity, two-sided smooth, then super with deionized water
Sound cleans 8min；Then it is immersed into the hydrofluoric acid that mass concentration is 25%, is taken out after ultrasonic 8min, then immerse deionization
In water, taken out after being cleaned by ultrasonic 8min
2) chemical plating: niobium foil is immersed into plating palladium liquid under conditions of 30 DEG C, plating obtains palladium-niobium-after sixty minutes
Palladium-based composite membrane；
Wherein, the plating palladium liquid be by palladium chloride, ammonium chloride, sodium hypophosphite and ammonium hydroxide and hydrochloric acid solution configuration and
At pH 7-10.And it plates in palladium liquid, palladium chloride (PdCl2) concentration be 4g/L, ammonium chloride (NH4Cl) concentration be 50g/L,
Sodium hypophosphite (NaH2PO2) concentration be 20g/L, 28% ammonium hydroxide (NH4OH) concentration is 200ml/L, and the hydrochloric acid solution that it is added
Mass concentration be 38% or so, specific additional amount (additional amount is about 2-6ml/L) and concentration and additional amount can carry out carefully
Micro- adjustment, so that its pH is subject to 7-10.
Embodiment 3
Present embodiments provide a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method, comprising the following steps:
1) it pre-processes: selecting the niobium film of thickness 0.25mm, be cut into 10 × 10mm size；It is two-sided successively using 280 to its
The SiC sand paper progress grinding process of mesh, 600 mesh, 1000 mesh and 1500 mesh, makes its two-sided grinding homogeneity, two-sided smooth, then spends
Ionized water is cleaned by ultrasonic 10min；Then it is immersed into the hydrofluoric acid that mass concentration is 29%, is taken out after ultrasonic 10min, then
It immerses in deionized water, is taken out after being cleaned by ultrasonic 10min；
2) chemical plating: niobium foil is immersed into plating palladium liquid under conditions of 30-80 DEG C, is obtained after plating 15-60 minutes
Palladium-niobium-palladium-based composite membrane；
Wherein, the plating palladium liquid be by palladium chloride, ammonium chloride, sodium hypophosphite and ammonium hydroxide and hydrochloric acid solution configuration and
At pH 7-10.And it plates in palladium liquid, palladium chloride (PdCl2) concentration be 2g/L, ammonium chloride (NH4Cl) concentration be 30g/L,
Sodium hypophosphite (NaH2PO2) concentration be 10g/L, 28% ammonium hydroxide (NH4OH) concentration is 150ml/L, and the hydrochloric acid solution that it is added
Mass concentration be 38% or so, specific additional amount (additional amount is about 2-6ml/L) and concentration and additional amount can carry out carefully
Micro- adjustment, so that its pH is subject to 7-10.
Embodiment 4
Present embodiments provide a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method, comprising the following steps:
1) it pre-processes: selecting the niobium film of thickness 0.25mm, be cut into 7 × 10mm size；It is two-sided successively using 280 to its
The SiC sand paper progress grinding process of mesh, 600 mesh, 1000 mesh and 1500 mesh, makes its two-sided grinding homogeneity, two-sided smooth, then spends
Ionized water is cleaned by ultrasonic 10min；Then it is immersed into the hydrofluoric acid that mass concentration is 29%, is taken out after ultrasonic 5min, then soak
Enter in deionized water, is taken out after being cleaned by ultrasonic 10min；
2) chemical plating: niobium foil is immersed into plating palladium liquid under conditions of 30-80 DEG C, is obtained after plating 15-60 minutes
Palladium-niobium-palladium-based composite membrane；
Wherein, the plating palladium liquid be by palladium chloride, ammonium chloride, sodium hypophosphite and ammonium hydroxide and hydrochloric acid solution configuration and
At pH 7-10.And it plates in palladium liquid, palladium chloride (PdCl2) concentration be 0.3-4g/L, ammonium chloride (NH4Cl) concentration is
10-50g/L, sodium hypophosphite (NaH2PO2) concentration be 2-20g/L, 28% ammonium hydroxide (NH4OH) concentration is 100-200ml/L, and
The mass concentration of its hydrochloric acid solution being added is 38% or so, specific additional amount (additional amount is about 2-6ml/L) and concentration
And additional amount can carry out subtle adjustment, so that its pH is subject to 7-10.
Palladium-niobium-palladium-based composite membrane is prepared using the preparation method of above-described embodiment, operates equal very simple, it is low in cost, and
It is environmental-friendly.Here, palladium-niobium-palladium-based composite membrane that embodiment 1 is obtained is scanned Electronic Speculum (SEM) observation, obtain such as figure
2 and figure shown in Fig. 3, the growth of plating palladium layers is fine and close known to observation, without obvious crackle, is well combined with niobium foil matrix, without falling off.
Element depth analysis is carried out to coating using Auger electron spectroscopy, obtains figure as shown in Figure 4, the thickness of plating palladium layers known to observation
About 2.4 μm of degree, oxygen element content is extremely low between palladium layers and matrix niobium, illustrates that pre-treatment step goes oxide layer in the present invention
Except effect is good (palladium-niobium-palladium-based composite membrane that other embodiments obtain is roughly the same with the testing result that embodiment 1 obtains).Thus
As it can be seen that palladium-niobium-palladium-based composite membrane that the present invention is prepared is it has also been found that its film surface layer is fine and close, covering is complete, nothing falls off, oxide layer
Removal effect is good, and prepared by the method palladium-niobium-palladium-based composite membrane has broad application prospects in Hydrogen Separation field.
Above-described embodiment is only one of the preferred embodiment of the present invention, should not be taken to limit protection model of the invention
It encloses, as long as that in body design thought of the invention and mentally makes has no the change of essential meaning or polishing, is solved
The technical issues of it is still consistent with the present invention, should all be included within protection scope of the present invention.
Claims (10)
1. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method, which is characterized in that first using mechanical rubbing method to niobium foil
It is pre-processed, removes the oxide layer of its outer surface, then niobium foil is immersed into plating palladium liquid under conditions of 30-80 DEG C, is applied
Palladium-niobium-palladium-based composite membrane is obtained after plating 15-60 minutes.
2. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method according to claim 1, which is characterized in that described pre-
Processing is then ultrasonic with deionized water the following steps are included: carry out outer surface polishing and planarizing process to niobium foil using SiC sand paper
Clean 5-10min；Then it is immersed into hydrofluoric acid, is taken out after ultrasonic 5-10min, then immerse in deionized water, ultrasound is clear
It is taken out after washing 5-10min.
3. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method according to claim 2, which is characterized in that use
It is successively to be come using the SiC sand paper of 280 mesh, 600 mesh, 1000 mesh and 1500 mesh when SiC sand paper carries out outer surface polishing to niobium foil
Polishing.
4. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method according to claim 3, which is characterized in that the hydrogen
The mass concentration of fluoric acid is 28%.
5. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method, feature described in any one according to claim 1~4
It is, the plating palladium liquid is to be mixed by soluble palladium salt, reducing agent, stabilizer and buffer, and hydrochloric acid solution tune is added
Whole its pH to 7-10.
6. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method according to claim 5, which is characterized in that the plating
Soluble palladium salt in palladium liquid is palladium chloride, and its concentration is 0.3-4g/L.
7. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method according to claim 6, which is characterized in that the plating
Reducing agent in palladium liquid is sodium hypophosphite, and its concentration is 2-20g/L.
8. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method according to claim 7, which is characterized in that the plating
Stabilizer in palladium liquid is ammonium chloride, and its concentration is 10-50g/L.
9. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method according to claim 8, which is characterized in that the plating
Buffer in palladium liquid is the ammonium hydroxide of mass concentration 28%, and concentration of the ammonium hydroxide in plating palladium liquid is 100-200ml/L.
10. a kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method according to claim 9, which is characterized in that described
The mass concentration of hydrochloric acid solution is 38%.
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| CN201811098585.XA CN109136893A (en) | 2018-09-20 | 2018-09-20 | A kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method |
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| CN201811098585.XA CN109136893A (en) | 2018-09-20 | 2018-09-20 | A kind of palladium-niobium-palladium-based composite membrane chemically plating Preparation Method |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002153740A (en) * | 2000-11-21 | 2002-05-28 | Mitsubishi Heavy Ind Ltd | Method of manufacturing pd-based hydrogen separation membrane |
| CN1644759A (en) * | 2004-12-16 | 2005-07-27 | 四川材料与工艺研究所 | Surface treating method for improving lanthanum alloy vapour impurity poisoning performance |
| CN103556140A (en) * | 2013-11-13 | 2014-02-05 | 北京达博有色金属焊料有限责任公司 | Palladium plating liquid for chemically preparing palladium-plated copper bonding wire |
| CN104911570A (en) * | 2015-05-14 | 2015-09-16 | 上海应用技术学院 | Plating solution carrying out chemical palladium plating on copper surface and preparation method therefor |
-
2018
- 2018-09-20 CN CN201811098585.XA patent/CN109136893A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002153740A (en) * | 2000-11-21 | 2002-05-28 | Mitsubishi Heavy Ind Ltd | Method of manufacturing pd-based hydrogen separation membrane |
| CN1644759A (en) * | 2004-12-16 | 2005-07-27 | 四川材料与工艺研究所 | Surface treating method for improving lanthanum alloy vapour impurity poisoning performance |
| CN103556140A (en) * | 2013-11-13 | 2014-02-05 | 北京达博有色金属焊料有限责任公司 | Palladium plating liquid for chemically preparing palladium-plated copper bonding wire |
| CN104911570A (en) * | 2015-05-14 | 2015-09-16 | 上海应用技术学院 | Plating solution carrying out chemical palladium plating on copper surface and preparation method therefor |
Non-Patent Citations (2)
| Title |
|---|
| FANGFANG LI ET AL.: "Effect of degassing treatment on the deuterium permeability of Pd-Nb-Pd composite membranes during deuterium permeation", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
| 刘菲等: "温度对化学镀钯层性能的影响", 《电镀与涂饰》 * |
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