CN102228800A - Method for washing load-type metal film - Google Patents
Method for washing load-type metal film Download PDFInfo
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- CN102228800A CN102228800A CN2011101686240A CN201110168624A CN102228800A CN 102228800 A CN102228800 A CN 102228800A CN 2011101686240 A CN2011101686240 A CN 2011101686240A CN 201110168624 A CN201110168624 A CN 201110168624A CN 102228800 A CN102228800 A CN 102228800A
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- metal film
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Abstract
The invention relates to a method for washing a load-type metal film, which is characterized in that the load-type metal film is placed in a diamine or formaldehyde solution with a certain concentration and subjected to heating in water bath; a cleanout fluid is replaced once at intervals; and the load-type metal film is washed repeatedly to be clean. The method is adopted to wash out various organisms and other impurities left on the metal film after metal deposition, thus preventing metal oxidation. The method is applied to washing the easily-oxidized load-type metal films and is strong in washing capacity and the metal films are not oxidized in the washing process. In the method, aiming at the degree of oxidation of the metals, cleaning solutions with different concentrations are used to improve the washing efficiency. The method has the characteristics of no foams, strong washing capacity, high efficiency, wide applied range and the like.
Description
Technical field
The present invention relates to a kind of preparation method of load type metal film, relate in particular to a kind of cleaning method of load type metal film, be specially adapted to the preparation of the load type metal or the alloy film of easy oxidation.
Background technology
Membrane separation technique is one of six big new and high technologies of 21 century.Than ceramic membrane and organic film, metal film has mechanical strength height, good heat conductivity, and easy advantage such as sealing, is widely used in fields such as electronics, machinery, biology, medical and health.Metal film can be divided into perforated membrane and dense film according to its pore structure, and the focus of metal current film research is porous metal film (as sintered stainless steel) and dense palladium and alloy film thereof.
Metal Palladium and alloy film thereof are to study the metal film that is applied to Hydrogen Separation the earliest, also may be to be applied to the unique business-like metal film that gas separates at present.Because self-support type palladium film cost height, the hydrogen flux is but very low, and the researcher just turns one's attention to brace type palladium film, attempts to seek the method that reduces its cost.Palladium is carried on porous matrix material can forms the load type palladium film, so not only reduced film thickness, saved precious metal palladium, and improved saturating hydrogen rate.
Pure palladium film is very limited in application owing to relatively poor, the easy hydrogen embrittlement of heat endurance, cost height.So the researcher introduces the palladium film with other metal, attempt to form the palladium alloy membrane that backing material is arranged of superior performance, as palladium-nickel, palladium-copper, palladium-silver alloy film etc.The load type palladium alloy film not only has anti-hydrogen embrittlement ability, oxidation resistance, excellent catalytic performance preferably, and have advantages such as favorable mechanical and heat endurance, therefore the saturating hydrogen performance of some palladium alloy membrane even also better than pure palladium film receives much concern in fields such as the separation of membrane reactor, hydrogen and purifying.
Now business-like palladium-silver film adopts the preparation of roll forming method, at first be that raw material is mixed according to a certain percentage, fusing at high temperature, obtain blank, after high-temperature heat treatment, again through cold pressing, hot rolling, forging, repeatedly rolling, annealing, finally obtain the film of desired thickness, the alloy film that this method makes need not to clean.
Usually, the preparation method of load type palladium and alloy film thereof has (Huang Yan etc., the progress of hydrogen permeation palladium-based composite membrane: principle, preparation and sign, chemical progress such as electroless plating method, galvanoplastic, physical vaporous deposition, chemical vapour deposition technique and sputtering method, 2006,18 (2-3): 230; Yu Jian etc., the pottery modification on porous stainless steel surface and the hydrogen permeating palladium membrane of institute's load, chemical progress, 2008,20 (7-8): 1208-1215).
The adoptable depositional mode of its metal of load type metal or alloy film has multiple, can adopt with a kind of preparation method's codeposition, also can adopt with a kind of preparation method to deposit step by step, can also adopt different preparation methods to deposit step by step certainly.The preparation process of load type metal and alloy film thereof generally comprises several steps such as matrix cleaning, plated film, post processing, wants the clean metal film usually in the last handling process, to obtain comparatively pure metal film.Palladium and alloy film thereof are very high to the requirement of purity, so the preparation of palladium and alloy film thereof is also very high to the requirement of cleaning.
The load type palladium and the alloy film thereof of the preparation of method such as chemical plating, plating owing to contain organic matters such as complexing agent, brightener in the plating bath, must clean repeatedly.Because these organic matters can decomposition under the high temperature, thereby oxidation forms number of C O, CH
4, impurity such as sulfide, influence the performance of alloy film.These organic matters also may decompose generation carbon during high-temperature process, attached to film surface or body mutually in, hinder the absorption of hydrogen, and carbon also may form Pd-C solid solution with palladium under proper condition, cause film to peel off (Kohji Yamakawa from the supporter easily, Michael Ege, Bernd Ludescher and Michael Hirscher, Surface adsorbed atoms suppressing hydrogen permeation of Pd membranes, J. Alloys Compd, 352 (2003) 57).
At present, normally use deionized water in 85 ~ 95 ℃ of water-baths, to clean sludge proof load type metal film repeatedly, at room temperature clean the load type metal film of easy oxidation with deionized water or ethanol.Though these methods can be used for the cleaning of metal film, if metal film contains the metal of easy oxidation, adopt above-mentioned two kinds of methods to clean and be easy to cause metal oxidized, and then change the component of film, finally influence the performance of film.For example, when cleaning the Cu film with deionized water or ethanol, Cu is easy to be oxidized to CuO, CuO again can with H
2O, CO
2Reaction generates Cu (OH)
2CO
3, this has not only changed the component of metal film, and can destroy the structure of film.Therefore, seek a kind of suitable cleaning method, for preparation load type metal film, especially easily oxidized load type metal film is necessary.Selected cleaning agent requires that cleansing power is strong, efficient is high and cleaning agent itself is removed easily.
Summary of the invention
The objective of the invention is when cleaning the load type metal film, to cause the oxidized problem of metal easily, proposed a kind of cleaning load type metal film, particularly the method for the load type metal film of easy oxidation in order to solve prior art.
Technical scheme of the present invention is:
A kind of cleaning method of load type metal film is with the rinsing repeatedly in cleaning fluid of load type metal film, it is characterized in that described cleaning fluid is the aqueous solution of diamine or formaldehyde, or their mixed solution.
In the load type metal film preparation process, finally influence the performance of film owing to the cleaning dirty pollution meeting that produces.Among the preparation technology of load type metal film, mainly be about 90 ℃, to clean the sludge proof metal film at present, at room temperature with the metal film of the easy oxidation of alcohol wash with deionized water.For the metal film of easy oxidation, usually easily with its surface oxidation, the weight of metal film also can change because of the oxidation of metal, thereby influences the calculating of film thickness with deionized water or alcohol wash.
The present invention utilizes diamine and formaldehyde to have the characteristics of reproducibility, post-depositional metal film is cleaned with diamine or formalin, can effectively prevent the oxidation of metal in the cleaning process, in case and the metal on film surface is oxidized in cleaning process, diamine in the cleaning fluid or formaldehyde can reduce metal oxide.The The Nomenclature Composition and Structure of Complexes that diamine that the present invention adopts or formalin can not change metal film, the performance that influences metal film, and cleaning force is strong, the cleaning process non-foam, itself easily removes.
The concrete operations step of described method is one of following dual mode:
A) load type metal film that will be to be washed is immersed in the container that adds the cleaning fluid I, heating, and every interval certain hour is changed cleaning fluid, and the repeated multiple times rinsing is cooled to room temperature, with the vacuum drying of load type metal film; The diamine aqueous solution that described cleaning fluid I is 0.002 ~ 0.0025 mol/L or the formalin of 0.04 ~ 0.05 mol/ L, or the mixed solution of 0.002 ~ 0.0025 mol/L diamine and 0.04 ~ 0.05 mol/L formaldehyde;
B) if the large-area metal oxidative phenomena appears in metallic film surface in the cleaning process, then earlier metal film is immersed in the cleaning fluid II, clean to the large tracts of land oxidative phenomena and disappear substantially, again A set by step) continue to clean; The diamine aqueous solution that described cleaning fluid II is 0.01 ~ 0.015 mol/L or the formalin of 0.2 ~ 0.25 mol/L, or the mixed solution of 0.01 ~ 0.015 mol/L diamine and 0.2 ~ 0.25 mol/L formaldehyde.
Described load type metal film comprises simple metal film or alloy film, preferred Cu, Ni, Al, Fe, Zn or Ag film, or comprise the alloy film of aforementioned metal.
Can be earlier in the cleaning with the metallic diaphragm of the new deposition of deionized water rinsing, and then place the container that cleaning fluid is housed to clean the metal film.A large amount of plating baths is contained in the metallic film surface of new deposition and inside, can remove most of plating bath with deionized water rinsing, has reduced the impurity content in the solution when cleaning, thereby has reduced wash number, has improved cleaning efficiency.
Cleaning process is carried out under heating condition, and preferred cleaning temperature is 85 ~ 95 ℃, and the cleaning performance in this temperature range is better, efficient is higher.Can adopt the water-bath mode of heating, be easy at cleaning process control cleaning temperature.
Cleaning method of the present invention with metal film rinsing repeatedly in the cleaning fluid of changing, is preferably changed a cleaning fluid every 25 ~ 30 min.Take all factors into consideration cleaning performance and cleaning efficiency, preferred about 8～12 h of scavenging period.
Before the present invention, when cleaning with deionized water or alcoholic solution, the metal of deposition, for example Cu, Ni etc. are easy to oxidized.Though the inventive method can not avoid occurring in the cleaning process phenomenon of burning fully, but diamine or methanol solution can original position reduce metal oxide in rinse cycle repeatedly, the metal that generates is deposited on film surface, can not influence the component and the structure of metal film.
For the different states of oxidation of the metal that occurs in the cleaning process, the inventive method is selected two kinds of different cleaning fluids for use.Not oxidized or surperficial when having fraction oxidized when metal film, directly clean with the cleaning fluid I, cleaning fluid I preferred concentration is the formalin of diamine solution or 0.04 ~ 0.05 mol/L of 0.002 ~ 0.0025 mol/L, perhaps their mixed liquor; Most of when oxidized when metallic film surface, clean to the large tracts of land oxidative phenomena with the cleaning fluid II earlier and disappear substantially, clean with the cleaning fluid I again, with the raising cleaning efficiency; Cleaning fluid II preferred concentration is the formalin of diamine solution or 0.2 ~ 0.25 mol/L of 0.01 ~ 0.015 mol/L, perhaps their mixed liquor.
Metal film is cooled to room temperature after cleaning, and removes cleaning fluid, puts into the vacuum drying chamber vacuum drying at last.
Beneficial effect of the present invention: the cleaning method of load type metal film of the present invention, especially obvious for the metal film cleaning performance of easy oxidation.Cleaning fluid washability of the present invention is strong, efficient is high, non-foam, applied range, and oxidized metal film is had very strong reproducibility, can prevent the oxidation of metal in the cleaning process, and not change the The Nomenclature Composition and Structure of Complexes of metal film.After the inventive method cleaning, metal film uniformity, brightness are all fine.Cleaning method of the present invention is used to prepare the load type palladium alloy film, not only residual organic in the metal film and other impurity can be removed, can also avoid the oxidation and the loss of plated film metal, the component of stable metal.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with the specific embodiment, but is limited by claim.
Description of drawings
Fig. 1 newly prepares the outward appearance picture on copper film surface.
The outward appearance picture on copper film surface after Fig. 2 washed with de-ionized water.
Fig. 3 diamine solution cleans the outward appearance picture on copper film surface, back.
Fig. 4 formalin is cleaned the outward appearance picture on copper film surface, back.
The specific embodiment
Embodiment 1 diamine solution cleans the chemical plating copper film
In the preparation process of load type palladium alloy film, adopt method of the present invention, clean the chemical plating copper film with diamine solution, final alloyization makes the palladium-copper alloy film.
(1) pre-treatment
The palladium film that chemical plating method is made places hydrochloric acid solution to soak half an hour, removes the pollutant that palladium film surface may exist, and then with washed with de-ionized water 1 h.
(2) electroless copper
Adopt chemical plating method at palladium film copper coating.Consisting of of plating bath: CuCl
22H
2O 8 g/L, KNaC
4H
4O
64H
2O 11 g/L, Na
2EDTA2H
2O 19 g/L, NaOH (28 %) 18g/L.Reducing agent is the formalin of 0.4 mol/L, and temperature is 60 ℃.
(3) clean
After electroless plating reaction finishes, several seconds of copper film that elder generation newly deposits with deionized water rinsing, copper film is placed test tube, the diamine solution that adds 0.002 ~ 0.0025 mol/L that has prepared to test tube, test tube is heated in water-bath then, at 85 ~ 95 ℃ of rinsing copper films repeatedly, change a cleaning fluid every 30 min, scavenging period is 12 h altogether.
(4) drying
After the cleaning copper film is placed vacuum drying chamber, be evacuated to negative pressure earlier, be heated to 120 ℃ then, reduce to room temperature after being incubated 15 h.
(5) alloying
With metal film at N
2Be warming up to 350 ℃ under the atmosphere, then at H
2Be warming up to 550 ℃ under the atmosphere,, form the palladium-copper alloy film at last at 550 ℃ of alloying 20 h.
Fig. 1 is seen on new preparation copper film surface.After adopting washed with de-ionized water before the present invention, the copper film appearance is seen Fig. 2, and adopts diamine solution to clean copper film surface, back as Fig. 3.Contrasted as seen by Fig. 1 to Fig. 3, freshly prepd copper film surface has a large amount of plating baths, contains impurity in the plating bath; After adopting washed with de-ionized water, dark spots or the zone that the oxidized back of metallic copper produces appears in the film surface, and adopt that the inventive method cleans after copper film, surface-brightening, color and luster are even.
Embodiment 2 formaldehyde clean the chemical plating copper film
In the preparation process of load type palladium alloy film, adopt method of the present invention, clean the chemical plating copper film with formalin, final alloyization makes the palladium-copper alloy film.
Method is with embodiment 1, and difference is that used cleaning fluid is the formalin of 0.01 ~ 0.015 mol/L in the step (3).
After formalin was cleaned, the outward appearance on copper film surface as shown in Figure 4.
Embodiment 3 diamines and formaldehyde mixed solution clean the chemical plating copper film
In the preparation process of load type palladium alloy film, adopt method of the present invention, clean the chemical plating copper film with diamine and formaldehyde mixed solution, final alloyization makes the palladium-copper alloy film.
Method is with embodiment 1, and difference is that used cleaning fluid is the diamine of 0.002 ~ 0.0025 mol/L and the formaldehyde mixed solution of 0.01 ~ 0.015 mol/L in the step (3).
Embodiment 4 diamines clean electroplating copper film
In the preparation process of load type palladium alloy film, adopt method of the present invention, clean electroplating copper film with diamine solution, final alloyization makes the palladium-copper alloy film.
(1) pre-treatment is with the step (1) of embodiment 1.
(2) electro-coppering
Adopt electro-plating method at palladium film copper coating.Consisting of of plating bath: CuSO
45H
2O 200 g/L, 50 %(wt) sulfuric acid 80 ml/L, wetting agent 2 ml/L.Electroplating temperature is 25 ℃, and current density is 3 ASD.
The cleaning of copper film, drying and alloying make the palladium-copper alloy film with step (3), (4), (5) of embodiment 1.
Embodiment 5 formaldehyde clean electroplating copper film
In the preparation process of load type palladium alloy film, adopt method of the present invention, clean electroplating copper film with formalin, final alloyization makes the palladium-copper alloy film.
Method is with embodiment 4, and difference is that used cleaning fluid is the formalin of 0.01 ~ 0.015 mol/L in the step (3).
Embodiment 6 diamines clean the electronickelling film
In the preparation process of load type palladium alloy film, adopt method of the present invention, clean the electronickelling film with diamine solution, final alloyization makes the palladium-nickel alloy film.
(1) pre-treatment is with the step (1) of embodiment 1.
(2) electronickelling
Adopt electro-plating method at palladium film plating nickel on surface.Consisting of of plating bath: nickel sulfamic acid 300 g/L, nickel chloride 60 g/L, boric acid 45 g/L, Spectra22 30 ml/L, Spectra311 2 ml/L, Wetting 1 ~ 2 ml/L current density 8 ASD, 65 ℃ of temperature.
The cleaning of nickel film, drying and alloying make the palladium-nickel alloy film with step (3), (4), (5) of embodiment 1.
Embodiment 7 formaldehyde clean the electronickelling film
In the preparation process of load type palladium alloy film, adopt method of the present invention, clean the electronickelling film with formalin, final alloyization makes the palladium-nickel alloy film.
Method is with embodiment 6, and difference is that used cleaning fluid is the formalin of 0.01 ~ 0.015 mol/L in the step (3).
The foregoing description helps the understanding of the present invention and enforcement, is not to be construed as limiting the invention.Enforcement the present invention also is not limited to the specific descriptions among the embodiment.Those skilled in the art can implement the present invention in different ways, for example the depositional mode of metal film is except that plating or chemical plating method, the metal film that can also comprise the easy oxidation that other depositional mode forms, perhaps the alloy film that forms of easy oxidation metal codeposition etc. can adopt cleaning method of the present invention equally.
Claims (6)
1. the cleaning method of a load type metal film is with the rinsing repeatedly in cleaning fluid of load type metal film, it is characterized in that described cleaning fluid is the aqueous solution of diamine or formaldehyde, or their mixed solution.
2. the cleaning method of load type metal film according to claim 1 is characterized in that cleaning step is one of following dual mode:
A) load type metal film that will be to be washed is immersed in the container that adds the cleaning fluid I, heating, every interval certain hour is changed cleaning fluid, the repeated multiple times rinsing, be cooled to room temperature after, with the vacuum drying of load type metal film;
B) if the large-area metal oxidative phenomena appears in metallic film surface in the cleaning process, then earlier metal film is immersed in the cleaning fluid II, clean to the large tracts of land oxidative phenomena and disappear substantially, again A set by step) continue to clean;
The diamine aqueous solution that described cleaning fluid I is 0.002 ~ 0.0025 mol/L or the formalin of 0.04 ~ 0.05 mol/ L, or the mixed solution of 0.002 ~ 0.0025 mol/L diamine and 0.04 ~ 0.05 mol/L formaldehyde;
The diamine aqueous solution that described cleaning fluid II is 0.01 ~ 0.015 mol/L or the formalin of 0.2 ~ 0.25 mol/L, or the mixed solution of 0.01 ~ 0.015 mol/L diamine and 0.2 ~ 0.25 mol/L formaldehyde.
3. the cleaning method of load type metal film according to claim 1 and 2 is characterized in that described load type metal film is support type Cu, Ni, Al, Fe, Zn, Ag simple metal film or alloy film.
4. the cleaning method of load type metal film according to claim 1 and 2 is characterized in that the temperature of cleaning is 85 ~ 95 ℃.
5. the cleaning method of load type metal film according to claim 1, be 25 ~ 30 min the blanking time that it is characterized in that changing cleaning fluid.
6. the cleaning method of load type metal film according to claim 1 is characterized in that scavenging period is 8～12 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823820A (en) * | 2017-03-03 | 2017-06-13 | 同济大学 | A kind of integrated apparatus for obtaining metal film operation and cleaning duty parameter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004122006A (en) * | 2002-10-03 | 2004-04-22 | National Institute Of Advanced Industrial & Technology | Hydrogen separation film, its production method and separation method for hydrogen |
| CN101041897A (en) * | 2007-04-29 | 2007-09-26 | 南京工业大学 | Chemical plating method for pipe porous material loading metal membrane |
| CN101054663A (en) * | 2007-05-29 | 2007-10-17 | 南京工业大学 | Activating process for nonmetal basal body chemical plating |
-
2011
- 2011-06-22 CN CN2011101686240A patent/CN102228800A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004122006A (en) * | 2002-10-03 | 2004-04-22 | National Institute Of Advanced Industrial & Technology | Hydrogen separation film, its production method and separation method for hydrogen |
| CN101041897A (en) * | 2007-04-29 | 2007-09-26 | 南京工业大学 | Chemical plating method for pipe porous material loading metal membrane |
| CN101054663A (en) * | 2007-05-29 | 2007-10-17 | 南京工业大学 | Activating process for nonmetal basal body chemical plating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823820A (en) * | 2017-03-03 | 2017-06-13 | 同济大学 | A kind of integrated apparatus for obtaining metal film operation and cleaning duty parameter |
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Application publication date: 20111102 |