CN103157389B - A kind of preparation method of asymmetric porous metal film - Google Patents
A kind of preparation method of asymmetric porous metal film Download PDFInfo
- Publication number
- CN103157389B CN103157389B CN201110414804.2A CN201110414804A CN103157389B CN 103157389 B CN103157389 B CN 103157389B CN 201110414804 A CN201110414804 A CN 201110414804A CN 103157389 B CN103157389 B CN 103157389B
- Authority
- CN
- China
- Prior art keywords
- porous metal
- preparation
- metal film
- asymmetric porous
- asymmetric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a kind of preparation method of asymmetric porous metal film, it is characterized in that in soluble metal salt solution, add reducing agent and dispersant, reducing metal ions is become metallic, under the effect of dispersant, form stable suspension; Obtained suspension is directly coated on porous metal matrix surface, sinters in protective atmosphere after drying, form asymmetric porous metal film.The preparation technology of metal microparticle introduces in film-forming process by the inventive method, wet chemistry method is obtained micro-/ nano spherical particle suspension directly as preparation liquid, the drying that can reduce metallic and dispersion process again, avoid the reunion of particle in preparation liquid, effective raising preparation liquid quality, reduce production craft step, save production cost.
Description
Technical field
The present invention relates to a kind of preparation method of porous composite film material, particularly relate to a kind of preparation method of asymmetric porous metal film.
Background technology
Along with the fast development of membrane science and technology, UF membrane has been widely used in the various fields such as the energy, petrochemical industry, biology, health medicine, environment, metallurgy and food as a kind of new and effective isolation technics.Compared with traditional isolation technics, membrane separation technique has efficient, energy-conservation, easy to operate, environmental friendliness and the advantage such as highly integrated.The membrane material that current industrial is applied mainly comprises inoranic membrane and organic film, and inoranic membrane is divided into again metal film and ceramic membrane.Wherein organic film to operating pressure and temperature requirement comparatively harsh, use under Acidity of Aikalinity condition for a long time and easily the irreversible deterioration such as hydrolysis occur, therefore its application is subject to larger restriction; Ceramic membrane applicability is well more a lot of than organic film, but its bad mechanical strength, sealing difficulty.In view of the shortcoming and defect of above-mentioned two kinds of membrane materials self, porous metal film receives increasing concern.
Compare with ceramic membrane with organic film, porous metal film has four large advantages:
1. mechanical strength is high, can use at elevated pressures, thus can improve permeability by the method increasing pressure reduction, improve the separating power of film.
2. there is good thermal conductivity performance and better heat-sinking capability, because this reducing the thermal stress of membrane module, thus improving the service life of film.
3. have good welding performance, membrane module is easy to connect.
4. be of very high actual application value.In membrane separating process, porous metal film adsorbance is large, and supportive is good, and filter area is large, can on-line cleaning, does not affect production.
Porous metal film mainly comprises the metal film such as Ag, Ni, Ti and stainless steel etc.Current stainless steel membrane is the porous metals membrane material that technology is comparatively ripe.Traditional porous stainless steel membrane can only reach coarse filtration level, and cannot meet the requirement that filtration flux is large and filtering accuracy is high simultaneously.And adopt the composite membrane of unsymmetric structure can solve this contradiction well, and the filtration grade of metal film can be improved.
The research of asymmetric metal film starts from the nineties in last century.It is generally made up of three parts: one is have high porosity, wide-aperture supporter (or matrix), and thickness is generally 2 – 3mm, and its effect is to provide enough physical strengths to support filter course; Two is have to filter optionally filter course (rete), generally thinner, and average pore size, below 1 μm, makes large particle be difficult to enter blocking filter road, filter membrane inside and be trapped in film surface; Three is the transition zones be between matrix and filter course, when matrix can not mate very well with the aperture of rete, needs there is a transition zone between matrix and rete, and makes two-layerly well to combine.
The preparation method of metal film mainly contains particles sintering method, thermal decomposition method and split-phase method etc.Wherein the application of particles sintering method is more, and preparation process is generally metal dust and suitable additives are mixed to form suspension and are coated on supporter, forms after drying through high temperature sintering.In sintering process, particle contacts with each other and is partly sintered together, and intergranular hole forms micropore.For the rete in obtained desirable aperture, the domain size distribution of metal-powder should be even, and be preferably regular spherical.In film-forming process, the pore-size distribution of rete is not only relevant with the size distribution of powder, and also closely related with the sintering condition of rete, powder can be micro/nano level, especially nano-powder has special small size and Large ratio surface effect, is easy to agglomeration occurs.In addition, the dispersed of nano-powder is also current problem demanding prompt solution.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of asymmetric porous metal film, metallic in porous metal film preparation process can be solved easily reunite, disperse uneven technical problem, the particle diameter of metallic particles and distribution in effective control metal film preparation process, obtained film surface is fine and close, uniform asymmetric porous metal film.
The present invention adopts following technical scheme:
A preparation method for asymmetric porous metal film, is characterized in that: in soluble metal salt solution, add reducing agent and dispersant, reducing metal ions is become metal simple-substance particle, under the effect of dispersant, form stable suspension; Obtained suspension is directly coated on porous metal matrix surface, sinters in protective atmosphere after drying, form asymmetric porous metal film.
The present invention adopts wet chemistry method one step directly obtained micro-/ nano spherical particle suspension, is directly coated on porous metal matrix as preparation liquid.After drying, asymmetric porous metal film is sintered to obtain.
The preparation technology of described asymmetric porous metal film, comprises following concrete steps:
(1) wet chemistry method prepares metallic suspension
In soluble metal salt solution, add a certain amount of reducing agent and dispersant, reaction generates metallic suspension under suitable conditions, and this suspension is directly as preparation liquid.
Described metal comprises silver, nickel, iron, titanium, palladium or copper.Described reducing agent be selected from ascorbic acid, sodium hypophosphite, hydrazine hydrate, potassium borohydride, urea, amine or aldehydes; Described dispersant mainly comprises polyvinylpyrrolidone, aniline, succinic acid, polyvinyl alcohol, gum arabic or naphthalenesulfonateformaldehyde formaldehyde sodium salt.
The preparation of suspension can refer to preparation technology's determination operation condition of metal microparticle in prior art.Usually, in described suspension, the mass concentration of metal ion is 0.05 ~ 1mol/l, and reducing agent consumption is 1 ~ 5 times of slaine molal weight, and dispersant dosage is 0.2 ~ 1wt% of solution quality.And adopt suitable jitter time and process for dispersing, usually adopt ultrasonic or high-speed stirred dispersion, ultrasonic disperse or mixing time are at 1 ~ 10h.
The particle diameter of the metallic that reduction obtains is 10 ~ 10000nm.
(2) preparation of film
By the metallic suspension of preparation, the technology such as dipping, spraying are adopted directly to be prepared in porous metal matrix surface, by controlling dipping number of times or spray coating liquor quality control thicknesses of layers, dry in an oven after drying, finally sinter in reducing atmosphere.
The aperture of described porous metal matrix is 0.5 ~ 10 times of metallic particle diameter, and its structure can select the asymmetric of uniform symmetric form or sandwich construction.
Sintering temperature is 300 ~ 1300 DEG C, and heating rate is 0.5 ~ 5 DEG C/min, and temperature retention time is 0.5 ~ 5h, sinters and carries out in inertia or reducing atmosphere.
Asymmetric porous metal film prepared according to the methods of the invention, according to the coupling between adopted porous metal matrix and filter course aperture, can also repeatedly adopt described method, first prepare the asymmetric metal film of sandwich construction, again with obtained asymmetric metal film for matrix, preparation is applicable to the asymmetric metal film in aperture.
Beneficial effect: the preparation method of asymmetric porous metal film of the present invention, wet chemistry method is obtained micro-/ nano spherical particle suspension directly as preparation liquid, the preparation technology of metal microparticle is directly introduced in film-forming process, the drying of preparing rete metallic and dispersion process again can be reduced, avoid the agglomeration traits of particle in preparation liquid, effective raising preparation liquid quality, reduces production craft step, saves production cost.Major advantage comprises:
(1) metal salt back is directly become metallic by the inventive method, and form stable suspension and carry out coating, decrease metallic particles dry with dispersion process again compared with common process, effectively prevent particle aggregation problem in suspension, reduce production cost.
(2) metallic prepared of the inventive method, particle diameter is little, be uniformly dispersed and easily control, and directly prepared rete, porous metal film surface uniform, defect is few.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope photo on asymmetric porous silverskin surface prepared by the inventive method.
Fig. 2 is the metallographic microscope photo of asymmetric porous silverskin section prepared by the inventive method.
Detailed description of the invention
Following examples are prepared as example with asymmetric porous silverskin, and described embodiment contributes to the understanding of the present invention and enforcement, is not construed as limiting the invention.Enforcement the present invention is also not limited to the specific descriptions in following examples; those skilled in the art can carry out equivalent or equivalent replacement or change to certain in embodiment or some technical characteristic, belong to the preparation method of the asymmetric porous metal film that the present invention protects equally.
Embodiment 1
Adopt the inventive method to prepare asymmetric silverskin, its concrete steps are as follows:
1) matrix selects diameter 20mm, thickness 3mm, the porous stainless steel disc of average pore size 2 μm, with stand-by after deionized water supersound washing, drying.
2) AgNO of 0.167mol/L is prepared
3with the ascorbic acid solution of 0.333mol/L, and in two solution, all add the gum arabic that mass fraction is 7%; Then with NaOH, ascorbic acid solution pH value is adjusted to 4 ~ 5, by AgNO
3solution joins in the ascorbic acid solution under magnetic agitation fast; At room temperature Keep agitation 24h.
3) be directly coated on porous stainless steel base by step 2 gained suspension, control thickness according to settling amount, 120 DEG C of dryings in an oven after normal temperature dries, then in a hydrogen atmosphere in 550 DEG C of sintering, heating rate is 2 DEG C/min, and temperature retention time is 2h.
The aperture adopting PSDA – 20 type Porosimetry to record asymmetric silverskin is 300nm.
Embodiment 2
Adopt the inventive method to prepare asymmetric silverskin, its concrete steps are as follows:
1) with asymmetric silverskin prepared in embodiment 1 for metallic matrix, with deionized water supersound washing, dry after stand-by.
2) AgNO of 0.6mol/L is prepared respectively
3and N
2h
4h
2o solution, and take 0.3gPVP and join AgNO
3stirring and dissolving in solution; Then by gained AgNO
3solution at a constant temperature, is added dropwise to N with the speed of 3ml/min
2h
4h
2in O solution, Keep agitation 30min.
3) by step 2 gained suspension on the material prepared by embodiment 1,120 DEG C of dryings in an oven after normal temperature dries, then in a hydrogen atmosphere in 350 DEG C of sintering, heating rate is 1 DEG C/min, and temperature retention time is 0.5h.
Adopting PSDA – 20 type Porosimetry to record aperture is 80nm.Its surface forms fine and close, uniform rete, (adopts field emission scanning electron microscope shooting) as shown in Figure 1; Cross-section photographs is (metallographic microscope shooting) as shown in Figure 2.
Embodiment 3
Adopt the present invention to prepare asymmetric copper film, its concrete steps are as follows:
1) matrix selects diameter 20mm, thickness 3mm, the porous stainless steel disc of average pore size 0.5 μm, with stand-by after deionized water supersound washing, drying.
2) CuSO of 0.2mol/L is prepared
4 .5H
2o solution, adds the aniline that mass fraction is 1%, mixes rear NaOH solution and its pH is adjusted to 11.5, then at the uniform velocity add the hydrazine hydrate solution of 3.0mol/L, and whole reaction stirs 2h at constant temperature lower magnetic force.
3) be directly coated on porous stainless steel base by step 2 gained suspension, control thickness according to settling amount, 120 DEG C of dryings in an oven after normal temperature dries, then in a hydrogen atmosphere in 750 DEG C of sintering, heating rate is 1 DEG C/min, and temperature retention time is 2h.
Adopting PSDA – 20 type Porosimetry to record aperture is 250nm.
Embodiment 4
Adopt the present invention to prepare asymmetric nickel film, its concrete steps are as follows:
1) matrix selects diameter 20mm, thickness 3mm, the porous stainless steel disc of average pore size 0.5 μm, with stand-by after deionized water supersound washing, drying.
2) certain density NiSO is first prepared
46H
2the N of O solution and certain mass mark
2h
4h
2o solution, joins N by appropriate PVP
2h
4h
2in O solution, after regulating pH by NaOH solution, at the uniform velocity add NiSO
46H
2o solution.Whole reaction stirs 30min at constant temperature lower magnetic force.
3) be directly coated on porous stainless steel base by step 2 gained suspension, control thickness according to settling amount, 120 DEG C of dryings in an oven after normal temperature dries, then in a hydrogen atmosphere in 950 DEG C of sintering, heating rate is 1 DEG C/min, and temperature retention time is 3h.
Adopting PSDA – 20 type Porosimetry to record aperture is 200nm.
Claims (7)
1. a preparation method for asymmetric porous metal film, is characterized in that: in soluble metal salt solution, add reducing agent and dispersant, reducing metal ions is become metal simple-substance particle, under the effect of dispersant, form stable suspension; Obtained suspension is directly coated on porous metal matrix surface, sinters in protective atmosphere after drying, form asymmetric porous metal film.
2. the preparation method of asymmetric porous metal film according to claim 1, is characterized in that described metal simple-substance is the one in silver, nickel, iron, titanium, palladium or copper.
3. the preparation method of asymmetric porous metal film according to claim 1, is characterized in that described reducing agent is ascorbic acid, sodium hypophosphite, hydrazine hydrate, potassium borohydride, urea, amine or aldehyde.
4. the preparation method of asymmetric porous metal film according to claim 1, is characterized in that described dispersant is the one in polyvinylpyrrolidone, aniline, succinic acid, polyvinyl alcohol, gum arabic or naphthalenesulfonateformaldehyde formaldehyde sodium salt.
5. the preparation method of asymmetric porous metal film according to claim 1, is characterized in that the particle diameter of described metal simple-substance particle is 10 ~ 10000nm.
6. the preparation method of asymmetric porous metal film according to claim 1, is characterized in that the aperture of described porous metal matrix is 0.5 ~ 10 times of metal simple-substance particle diameter, and its structure is the asymmetric of uniform symmetric form or sandwich construction.
7. the preparation method of asymmetric porous metal film according to claim 1, it is characterized in that described sintering temperature is 300 ~ 1200 DEG C, heating rate is 0.5 ~ 5 DEG C/min, and temperature retention time is 0.5 ~ 5h, sinters and carries out in inertia or reducing atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110414804.2A CN103157389B (en) | 2011-12-14 | 2011-12-14 | A kind of preparation method of asymmetric porous metal film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110414804.2A CN103157389B (en) | 2011-12-14 | 2011-12-14 | A kind of preparation method of asymmetric porous metal film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103157389A CN103157389A (en) | 2013-06-19 |
| CN103157389B true CN103157389B (en) | 2016-03-02 |
Family
ID=48581228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110414804.2A Active CN103157389B (en) | 2011-12-14 | 2011-12-14 | A kind of preparation method of asymmetric porous metal film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103157389B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357876A (en) * | 2013-07-29 | 2013-10-23 | 西北有色金属研究院 | Preparation method for nano multihole copper film |
| CN103691329B (en) * | 2013-12-20 | 2016-01-20 | 南京工业大学 | Preparation method of porous stainless steel membrane |
| CN105597553A (en) * | 2016-03-17 | 2016-05-25 | 江苏久吾高科技股份有限公司 | Preparation method of ceramic membrane used in membrane absorption process |
| CN108436100B (en) * | 2018-04-09 | 2021-06-04 | 哈尔滨工业大学（深圳） | Preparation method of ultrathin porous nano nickel foil |
| CN114289720B (en) * | 2021-11-30 | 2023-09-29 | 成都易态科技有限公司 | Preparation method of green body and sintered porous metal film and dust removal method |
| CN114523108B (en) * | 2021-11-30 | 2023-09-29 | 成都易态科技有限公司 | Blank, sintered porous metal film and dust removal method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB927285A (en) * | 1958-08-30 | 1963-05-29 | Commissariat Energie Atomique | A new or improved process for the manufacture of microporous metallic membranes |
| CN1150060A (en) * | 1995-11-14 | 1997-05-21 | 中国科学院大连化学物理研究所 | Process for preparing metal-ceramic composite film by chemical plating |
| US6228426B1 (en) * | 1998-10-19 | 2001-05-08 | Korea Research Institute Of Chemical Technology | Process for preparing composite inorganic membranes |
| CN1843597A (en) * | 2006-04-07 | 2006-10-11 | 陈明波 | A novel metal filtration film and preparation method thereof |
| CN1929900A (en) * | 2004-01-09 | 2007-03-14 | 英国石油有限公司 | Metallic palladium composite membrane or alloy palladium composite membrane and method for their preparations |
| CN101234296A (en) * | 2008-02-29 | 2008-08-06 | 南京工业大学 | Preparation process of porous stainless steel-ceramic composite membrane |
| CN101568373A (en) * | 2006-11-08 | 2009-10-28 | 国际壳牌研究有限公司 | A gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use |
-
2011
- 2011-12-14 CN CN201110414804.2A patent/CN103157389B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB927285A (en) * | 1958-08-30 | 1963-05-29 | Commissariat Energie Atomique | A new or improved process for the manufacture of microporous metallic membranes |
| CN1150060A (en) * | 1995-11-14 | 1997-05-21 | 中国科学院大连化学物理研究所 | Process for preparing metal-ceramic composite film by chemical plating |
| US6228426B1 (en) * | 1998-10-19 | 2001-05-08 | Korea Research Institute Of Chemical Technology | Process for preparing composite inorganic membranes |
| CN1929900A (en) * | 2004-01-09 | 2007-03-14 | 英国石油有限公司 | Metallic palladium composite membrane or alloy palladium composite membrane and method for their preparations |
| CN1843597A (en) * | 2006-04-07 | 2006-10-11 | 陈明波 | A novel metal filtration film and preparation method thereof |
| CN101568373A (en) * | 2006-11-08 | 2009-10-28 | 国际壳牌研究有限公司 | A gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use |
| CN101234296A (en) * | 2008-02-29 | 2008-08-06 | 南京工业大学 | Preparation process of porous stainless steel-ceramic composite membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103157389A (en) | 2013-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103157389B (en) | A kind of preparation method of asymmetric porous metal film | |
| CN103695689B (en) | A kind of preparation method of Fe-Al series intermetallic compound perforated membrane | |
| CN102958630B (en) | Method for producing core-shell magnetic alloy nanoparticle | |
| CN101439305B (en) | Composite material using nano inorganic powder as surface with autocatalytic activity and preparation method thereof | |
| CN104815651B (en) | Preparation method of precious metal/titanium dioxide nano composite | |
| CN101358304A (en) | NiAl intermetallic compound porous material and preparation method thereof | |
| CN111020329B (en) | Method for preparing porous tungsten material based on W-Fe-C system corrosion method | |
| CN108188400A (en) | A kind of micro-nano twin-stage Porous Cu and preparation method thereof | |
| CN105648260A (en) | Method for preparing micrometer porous metal copper blocks by dealloying of copper-ferrum alloy | |
| CN109745870A (en) | A kind of preparation method of porous metal film | |
| CN104646025A (en) | Preparation method of hollow Pt/Ni alloy and graphene aerogel compound material | |
| CN106623975B (en) | A kind of nanoscale platinum-rhodium alloy powder and preparation method thereof | |
| CN109692971A (en) | A kind of nano-silver powder and its preparation and the application in low-temperature cured conductive silver paste | |
| CN102672168B (en) | Preparation method for core-shell structural nickel-silver bimetallic powder | |
| CN108149048A (en) | Micro-nano twin-stage Porous Cu and preparation method thereof | |
| CN102554218A (en) | Method for preparing tungsten-copper composite powder by means of electroless copper plating | |
| CN105803239A (en) | Preparation method for micro-pore-diameter high-porosity nickel-chrome-molybdenum porous material | |
| CN105728716A (en) | Core-shell type metal graphite composite powder material and preparation method thereof | |
| CN108706568A (en) | A kind of preparation method of N doping Porous hollow carbon Nano capsule material and the material of preparation | |
| CN104131194B (en) | A kind of preparation method of micropore aluminum or aluminum alloy | |
| CN106311227A (en) | Synthetic method of material with palladium particles loaded on three-dimensional macroporous molybdenum dioxide | |
| CN104988476A (en) | Method for plating nano-silver on surface of diamond micro-powder | |
| CN102389715B (en) | Method for preparing porous inorganic membrane by carbon skeleton-assisted particle sintering process | |
| CN109454231A (en) | A kind of preparation method of iron aluminium copper micropore filter material | |
| CN117563328A (en) | PE sintered filter element film-coating material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |