CN103031581A - Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas - Google Patents
Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas Download PDFInfo
- Publication number
- CN103031581A CN103031581A CN2012100457094A CN201210045709A CN103031581A CN 103031581 A CN103031581 A CN 103031581A CN 2012100457094 A CN2012100457094 A CN 2012100457094A CN 201210045709 A CN201210045709 A CN 201210045709A CN 103031581 A CN103031581 A CN 103031581A
- Authority
- CN
- China
- Prior art keywords
- film
- liquid phase
- metal
- multicarbide
- plasma
- 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.)
- Pending
Links
Abstract
The invention relates to the technical field of carbide film preparation and particularly relates to a technological method of preparing a metal/semimetal/nonmetallic multi-element carbide film through electrodeposition of liquid phase plasmas. The technological method is characterized by comprising the steps that components such as carbon sources and element precursors to be plated are contained in an organic solution or an aqueous solution, a maximum value of a voltage needed by activating and ionizing each element precursor component to be plated into plasmas is used as an operation voltage, the operating temperature is 20-100 DEG C, the current density is 10-500mA/cm2, the area ratio of a cathode to an anode is 1:(1-2), a distance between electrodes is 5-50mm, any one of conductive materials or materials with conductive layers functions as the cathode (substrate), the element precursors to be plated in bubbles in cathode and anode regions are ionized to produce the plasmas through the action of high voltage, and the plasmas deposit on the surface of the cathode to obtain the multi-element carbide film. According to the method, the operation is conducted at low temperature and in constant pressure, a technology and equipment are simple, the operation is easy, the finished product rate is high, the cost is low and the industrial production is easy.
Description
Technical field
The present invention relates to carbide thin film material preparation technical field, refer to that specifically a kind of liquid phase plasma galvanic deposit prepares the processing method of the multicarbide thin-film material of metal/semiconductor metal/non-metal.
Background technology
Carbide occupies the status of particularly important in superhard material, the carbide thin film type is very similar to nitride with character, can form carbide with IV family, V family and VI family element, also can form carbide with boron, silicon.Has hardness (26 GPa ~ 31 GPa) and the performances such as fusing point is high, wear-resistant and corrosion resistance is good, low friction, thermal conductivity is good, chemical stability is excellent such as the TiC film.
At present, the method for preparing film is generally chemical Vapor deposition process and physical vaporous deposition, prepares the metallic carbide film such as US Patent No. P 7,611,751 by vapour deposition process and ald (ALD) technology.US Patent No. P 5,061, and 514 prepare the silicon-carbon film at matrix with plasma (orifice) gas phase chemistry vapour deposition process.Chinese patent CN100506527C adopts magnetron sputtering technique and ion beam technology to prepare the nano-multilayer film of metallic carbide (intermediate layer).Chinese patent CN101073841A produces the beam-plasma deposited metal carbide coatings (matrix is cutter head) of metal ion and carbon ion from cathodic vacuum arc source under rare gas element or vacuum.The carbon thermodiffusion that Chinese patent CN03114441.1 utilizes alloy substrate inside is in prefabricated alloy coat and be translated into carbide coating.Chinese patent CN 200410079505.8 uses B in fused borax bath
4The flue dust that the C powder reduction contains vanadium (or chromium or titanium or niobium) oxide compound obtains containing vanadium (or chromium or titanium or niobium) carbide coating.
Yet vapour deposition process prepares film and has some limitations, and is too high such as the depositing temperature of chemical vapour deposition (CVD), and general base material is difficult to bear, and internal stress is larger between film/base; Though evaporation or sputtering method depositing temperature are lower than CVD, rete is loose porous, poor mechanical property, and film/basic interface bond strength is low; Multi-arc ion coating sprays unstable, and film surface is coarse, short texture; Vapour deposition process needs vacuum operating, the equipment complex and expensive, and energy consumption is large, and cost is high, and sedimentation rate is low, and object plating face is limited; Vapour deposition process does not usually reach and is difficult to control essential stoichiometric ratio, causes film performance not reach requirement etc.
Namba (Y J Namba.Vac.Sci.Technol.A, 1992,10:3368) at first under liquid phase and cold condition, adopt high-voltage electrolysis ethanolic soln to obtain amorphous carbon film, since then, the emerging technology that liquid phase plasma galvanic deposit/plating is processed as a kind of material surface arouses widespread concern.Such as people (I Suzuli, Y Mantia, T Yamazaki, et al. J. Mater.Sci., 1995,30:2067 such as report Suzuki in the document; H Wang, M R Shen, Z Y Ning, et al. Thin Solid Films, 1997,293:87; Fu Q, Jiu J T, Cao C B, Surf. Coat. Technol., 2000,124:196; A L Yerokhin, X Nie, A Leyland, et al. Surf. Coat. Technol., 2000,130:195) in succession the aspects such as liquid electrodeposition quasi-diamond and film ceramic film are studied; US Patent No. P 7,166,206(Chen Z. P. Plasma electroplating. USP 7,166,206,2007-1-23) introduce under condition of normal pressure, between negative electrode and positive electrode, apply high-voltage, so that bubble area produces glow discharge, in bubble, produce plasma body by the ionized gas molecule, realize that material (comprising metal and nonmetal) is in the deposition of electrode surface; US Patent No. P 6,368,467 (Electro-plating plasma arc deposition process.USP 6,368,467 2002-4-9) in the electrolytical aqueous solution of containing metal, effect by volts DS produces plasma arc, obtains required metallic membrane at cathode surface.
The preparation method of liquid phase plasma electrodeposited film has many outstanding characteristics, its technique and the similar general electro-deposition system of device, do not need vacuum apparatus, cost is very low, technique and simple to operate, service temperature is significantly less than CVD (Chemical Vapor Deposition) method, can avoid the hot conditions of CVD (Chemical Vapor Deposition) method on the impact of body material, reduce internal stress, increase the bonding strength of film/base, widen the selection range of matrix, can also be on complex-shaped matrix uniform big area film forming, be well suited for suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of liquid phase plasma galvanic deposit to prepare the processing method of multicarbide ganoine thin film, enlarged the range of application of liquid phase plasma electro-deposition techniques, the multicarbide film both can be mechanically resistant material, also can be used as the transition layer of multilayer film.Secondly, by the selection to component in the multicarbide film, improve the bonding strength of film/base, reduce the internal stress of rete, can widen the selection range to body material.Its three, the low temperature liquid phase plasma electrically deposits the stoichiometric relation that is beneficial to control multicarbide film, can avoid vapour deposition to be difficult to control the problem of quantitative relation between each component of film.By the red-tape operati condition, can regulate easily the quantitative relation between each component, make hard films reach best performance, and good reproducibility.Its four, the liquid phase plasma galvanic deposit can obtain the deposition potential element more negative than hydrogen, has enlarged widely the selection of multicarbide film composition.This law equipment is simple, the low-temperature atmosphere-pressure operation, and working condition is gentle, and technical process is simple, processing ease, yield rate is high, and cost is low.Thereby the present invention has a extensive future.
The technological process that liquid phase plasma galvanic deposit of the present invention prepares carbide is:
Experiment is to carry out under the low-temperature atmosphere-pressure condition, take high-purity carbon-point or metallic titanium plate or platinized platinum as anode, take the metallic substance such as stainless steel plate or titanium plate or conductive plastics as negative electrode, contains the components such as carbon source and element precursor to be plated in the electrolytic solution.The electrolytic solution of anode and cathode near zone is under action of high voltage, and electrolysis forms group of bubble family.When voltage reached a certain particular value, so that bubble area produces glow discharge, element precursor to be plated and the carbon source of gasification were subject to electron puncture in the bubble, form the plasma body of ionized gas molecule.Plasma body obtains high-energy in argon-arc plasma field, cross the interface energy barrier under the effect of extra electric field power, is deposited on electrode (matrix) surface.At this moment, control is stablized high-voltage in the interval of glow discharge, and keeps bubble area glow discharge for some time, then takes out negative plate and rinses well, and drying can obtain the multicarbide thin-film material at workpiece (negative electrode) surface deposition.
Pre-treatment need be carried out in workpiece (negative electrode) surface before liquid phase plasma galvanic deposit operation, comprise purifying and etching, polishes etc., can be with reference to conventional galvanic deposit job specification, comprise that alkali cleaning oil removing and pickling derust, and electrolytic etching etc.
The outer configurable heating installation of electrolyzer keeps the required temperature of experiment in the operating process heating.Condenser is equipped with in the electrolyzer top, is used for the steam of condensing reflux solvent.In addition, the liquid phase plasma electric deposition device is furnished with fluid infusion system, according to circumstances replenishes electrolytic solution to electrolyzer.
The components such as electrolyte component carbonaceous sources of the present invention, element precursor to be plated, solvent, conducting salt, suds booster, tensio-active agent.
Precursor comprises low-molecular-weight organism, metallic salt, organometallics class, organometallic compound class, inorganics class etc.Each precursor component of multicarbide provides deposition required plasma source.
The selection principle of the precursor of multicarbide: soluble in water or organic solvent, easily vaporization, higher specific inductivity and specific conductivity, the easy breakdown disassociation of gaseous state, easily be excited to be in excited state and form active group.
The precursor of multicarbide also can be according to the voltage-current characteristic Curve selection.By voltage-current characteristic experiment, judge that precursor produces the condition of plasma body, complexity, voltage swing is determined the precursor of each component.
Also can add additive, the tensio-active agent (suds booster) that reduces electrolyte surface tension force that improves electrolytic conductivity, catalyzer class additive, the additive that improves quality of coating, the pH value buffer reagent that improves sedimentation rate in the electrolytic solution.In electrolytic solution, can add in these components one or more.The additive that improves electrolytic conductivity has inorganic salt or organic salt.
Body material of the present invention (substrate material of negative electrode or negative electrode) can be arbitrary electro-conductive material or with the material of conductive layer, such as aluminium alloy, stainless steel, rapid steel, Wimet, titanium alloy, silicon chip, conductive glass, conductive plastics and other metal or alloy materials etc.
Anode material is mainly high-purity carbon-point, titanium plate, stainless steel plate, platinized platinum etc.
Ratio of cathodic to anodic area is 1:1 ~ 2, and preferred ratio of cathodic to anodic area is 1:1.The interpole gap of anode and cathode is 5mm ~ 50 mm.Preferred interpole gap is about 10mm ~ 20mm.
The processing condition of liquid phase plasma galvanic deposit operation of the present invention mainly contain voltage, current density, temperature, pressure etc.
Be applied to two interelectrode voltages and will satisfy all intensified plasma bodys that is ionized into of all precursor component to be plated, it is next definite that concrete value can be done experiment, gets the maximum that each component produces the plasma body required voltage.Also can pass through the size of voltage-current characteristic Curve selection operating voltage, and determine according to its maximum.
The service temperature of liquid phase plasma galvanic deposit remains on 20 ℃ ~ 100 ℃, and actual service temperature will be determined with the situation that electrolytic solution produces bubble, generally be preferably 50 ℃ ~ 70 ℃.
The current density of liquid phase plasma galvanic deposit of the present invention is 10mA/cm
2~ 500mA/cm
2, be preferably 50mA/cm
2~ 200mA/cm
2
Liquid phase plasma galvanic deposit of the present invention operates under the normal pressure to be carried out, and normally working pressure is about 1atm.
DC high-voltage power supply is adopted in the operation of liquid phase plasma galvanic deposit of the present invention, and voltage range 0 ~ 5000V is adjustable, and range of current 0 ~ 3A is adjustable, also can adopt the pulse direct current high-voltage power supply.
Compared with prior art, the present invention has following advantage
1. the liquid phase plasma galvanic deposit technology for preparing the multicarbide film is conducive to control stoichiometric relation, and can increase and decrease easily the rete component and regulate the quantitative relation of film layer group between dividing by control processing condition and electrolyte component, make hard films reach best performance, and good reproducibility can also be controlled film thickness.
2. cold operation, working condition are relatively gentle, can overcome the hot conditions of CVD (Chemical Vapor Deposition) method to the impact of body material, have widened the range of choice of base material, can reduce the internal stress between the film base, increase bonding strength, improve film quality;
3. technique of the present invention and the similar general electro-deposition system of device, atmospheric operation does not need vacuum apparatus, work simplification, cost is well suited for suitability for industrialized production, can also be on complex-shaped matrix Large-Area-Uniform deposition film forming.
4. plasma electroplating belongs to non-faraday district's plating, the deposition potential element (metal and nonmetal) more negative than hydrogen all can obtain by the liquid phase plasma galvanic deposit, expand widely the selection of multicarbide film composition, also enlarged the scope that base material is selected.
Specific embodiments
Embodiment 1
1. the concrete component of electrolytic solution is: ethanol 85 g/L, metallorganics titanium propanolate (TPT) 32 g/L, conducting salt 20 g/L, tensio-active agent 0.02 g/L.Tensio-active agent is any in succsinic acid, Sodium dodecylbenzene sulfonate, the sodium lauryl sulphate etc.A kind of in the optional inorganic salt of conducting salt or the organic salt.
2. the processing parameter of galvanic deposit is: DC high-voltage power supply, and voltage across poles 1500 V ~ 2000 V, current density is 30mA/cm
2~ 80mA/cm
2, system is atmospheric operation, pH neutral range, temperature 50 C ~ 60 ℃.Depositing time 120 min ~ 180 min.
3. negative electrode adopts stainless steel plate, and anode is Ir oxide coating titanium plate, ratio of cathodic to anodic area 1:1, cathode and anode spacing 10 mm ~ 15 mm.
Embodiment 2
1. the concrete component of electrolytic solution is: methane amide 40 g/L, metallorganics titanium propanolate (TPT) 25 g/L, dimethyldiethoxysilane 20 g/L, methyl alcohol 60 g/L.Conducting salt 20 g/L, tensio-active agent 0.02 g/L.Tensio-active agent and conducting salt are with embodiment 1.
2. the processing parameter of galvanic deposit is: the high frequency pulse dc high-voltage power supply, and voltage 1500 V ~ 2000 V, pulse duty factor is 80%, operating pressure is normal pressure, pH neutral range, temperature 60 C ~ 70 ℃.Depositing time 180 min ~ 240 min.
3. negative electrode adopts the titanium plate, and anode is the high purity graphite sheet, ratio of cathodic to anodic area 1:1, cathode and anode spacing 10 mm ~ 15 mm.
Multicarbide film to the embodiment preparation adopts energy spectrometer (EDS), X X-ray photoelectron spectroscopy X (XPS), x-ray diffractometer (XRD), nanometer press fit instrument, friction and wear tester to carry out analysis and characterization, the result shows thickness 800 nm～3 μ m, and titanium content is about 43.2 at.%; The C of TiC film
1SThe 1s electron binding energy of being combined with Ti in the spectrum is at 281.9eV, Ti
2pBe combined the Ti that generates TiC in the spectrum with C
2p3/2Electron binding energy is positioned at about 455.0eV; Located three diffraction peaks for 35.9 °, 41.7 ° and 60.6 ° on the XRD collection of illustrative plates, corresponded respectively to (111) of TiC, (200) and (220) crystal face, take the TiC of fcc structure mutually as main; The consistency and elasticity modulus of TiC film is about 34 GPa and 350 GPa, and frictional coefficient is about 0.25.
Claims (10)
1. a liquid phase plasma galvanic deposit prepares the processing method of multicarbide thin-film material, it is characterized in that the using plasma electro-deposition techniques prepares the carbide thin film of multicomponent mixture under liquid phase electrolyte solution and low-temperature atmosphere-pressure condition.
2. the composition that according to claim 1, it is characterized in that multicarbide (MxC) film can be metallic element or semimetallic elements or non-metallic element.
3. according to claim 2, it is characterized in that multicarbide (MxC) film can be metal-carbon compound film, semi-metal-carbide thin film, nonmetal-carbide thin film, metal-semi-metal-carbide thin film, metal-nonmetal-carbide thin film.
4. according to claim 1, it is characterized in that the multicarbide film can be binary carbide films, or the double carbide film, or the multicarbide film.
5. according to claim 1, it is characterized in that the liquid phase electrolyte solution is organic solution or the aqueous solution, the precursor of element to be plated is metal-salt, organometallics, organometallic compound, organism, inorganics.
6. the voltage across poles that according to claim 1, it is characterized in that the liquid phase plasma galvanic deposit is determined according to the intensified maximum that is ionized into the plasma body required voltage of each component of precursor to be plated in the electrolytic solution.
7. according to claim 1, it is characterized in that as body material (substrate material of negative electrode or negative electrode) can be arbitrary electro-conductive material or with the material of conductive layer, such as aluminium alloy, stainless steel, rapid steel, Wimet, titanium alloy, silicon chip, conductive glass, conductive plastics and other metal or alloy materials etc.
8. according to claim 1, it is characterized in that ratio of cathodic to anodic area is 1:1 ~ 2, interpole gap is 5mm ~ 50 mm, and preferred interpole gap is about 10mm ~ 20mm.
9. according to claim 1, it is characterized in that the temperature of electrolytic solution in the liquid phase plasma electrodeposition process remains on 20 ℃ ~ 100 ℃, be preferably 50 ℃ ~ 70 ℃.
10. according to claim 1, it is characterized in that current density is 10mA/cm in the liquid phase plasma electrodeposition process
2~ 500mA/cm
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100457094A CN103031581A (en) | 2012-02-27 | 2012-02-27 | Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100457094A CN103031581A (en) | 2012-02-27 | 2012-02-27 | Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103031581A true CN103031581A (en) | 2013-04-10 |
Family
ID=48018964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100457094A Pending CN103031581A (en) | 2012-02-27 | 2012-02-27 | Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103031581A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484928A (en) * | 2013-10-09 | 2014-01-01 | 电子科技大学 | Plasma-based steel product derusting polishing method |
| CN105543925A (en) * | 2015-12-24 | 2016-05-04 | 斌源材料科技（上海）有限公司 | Electrolytic solution based on carbonaceous mesophase and method for preparing carbon membrane from electrolytic solution |
| CN105568341A (en) * | 2016-02-22 | 2016-05-11 | 深圳市威勒科技股份限公司 | Tungsten oxide thin film and preparation method thereof |
| CN108147831A (en) * | 2016-12-06 | 2018-06-12 | 航天特种材料及工艺技术研究所 | A kind of preparation method of C/C composite materials high-temperature oxidation resistant coating |
| CN109055933A (en) * | 2018-09-04 | 2018-12-21 | 北京理工大学 | A kind of powder liquid phase plasma surface modifying method and its device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256327A (en) * | 1999-11-22 | 2000-06-14 | 北京理工大学 | Electrochemical deposition process to prepare hard film |
| CN1632177A (en) * | 2003-12-24 | 2005-06-29 | 中国科学院兰州化学物理研究所 | Process for preparing carbon-nitrogen film containing crystal structure |
| CN1796612A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Method for preparing composite film of carbon similar to generic diamond containing Nano granules of silicon dioxide |
| CN101736379A (en) * | 2008-11-22 | 2010-06-16 | 中国科学院兰州化学物理研究所 | Preparation method of super-hydrophilic diamond-like carbon composite film |
-
2012
- 2012-02-27 CN CN2012100457094A patent/CN103031581A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256327A (en) * | 1999-11-22 | 2000-06-14 | 北京理工大学 | Electrochemical deposition process to prepare hard film |
| CN1632177A (en) * | 2003-12-24 | 2005-06-29 | 中国科学院兰州化学物理研究所 | Process for preparing carbon-nitrogen film containing crystal structure |
| CN1796612A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Method for preparing composite film of carbon similar to generic diamond containing Nano granules of silicon dioxide |
| CN101736379A (en) * | 2008-11-22 | 2010-06-16 | 中国科学院兰州化学物理研究所 | Preparation method of super-hydrophilic diamond-like carbon composite film |
Non-Patent Citations (1)
| Title |
|---|
| FENG HUANG等: "The Preparation and Microstructure of DLC Films Deposited through Plasma Electrodeposition in Water/Ethanol Solution", 《ADVANCED MATERIALS REARCH》, vol. 750752, 31 December 2013 (2013-12-31), pages 2003 - 2007 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484928A (en) * | 2013-10-09 | 2014-01-01 | 电子科技大学 | Plasma-based steel product derusting polishing method |
| CN103484928B (en) * | 2013-10-09 | 2016-03-23 | 电子科技大学 | A kind of rust cleaning of the steel product based on plasma body finishing method |
| CN105543925A (en) * | 2015-12-24 | 2016-05-04 | 斌源材料科技（上海）有限公司 | Electrolytic solution based on carbonaceous mesophase and method for preparing carbon membrane from electrolytic solution |
| CN105543925B (en) * | 2015-12-24 | 2018-02-02 | 斌源材料科技（上海）有限公司 | A kind of electrolyte based on Carbonaceous mesophase and its method for preparing carbon film |
| CN105568341A (en) * | 2016-02-22 | 2016-05-11 | 深圳市威勒科技股份限公司 | Tungsten oxide thin film and preparation method thereof |
| CN105568341B (en) * | 2016-02-22 | 2018-08-03 | 深圳市威勒科技股份限公司 | A kind of tungsten oxide film and preparation method thereof |
| CN108147831A (en) * | 2016-12-06 | 2018-06-12 | 航天特种材料及工艺技术研究所 | A kind of preparation method of C/C composite materials high-temperature oxidation resistant coating |
| CN108147831B (en) * | 2016-12-06 | 2020-06-12 | 航天特种材料及工艺技术研究所 | Preparation method of C/C composite material high-temperature oxidation-resistant coating |
| CN109055933A (en) * | 2018-09-04 | 2018-12-21 | 北京理工大学 | A kind of powder liquid phase plasma surface modifying method and its device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103339298B (en) | Non-metallic coating and method of its production | |
| Devilliers et al. | Cr (III) oxidation with lead dioxide-based anodes | |
| JP5923478B2 (en) | Laminated structure | |
| CN103031581A (en) | Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas | |
| CN103014793B (en) | Method for preparing titanium carbide coating through pulse electrodeposition | |
| CN104164690B (en) | Cathode plasma electrolysis extensive deposition coating and the method for surface modification | |
| CN101003909A (en) | Electrochemical combined deposition method for preparing structure of composite membrane of Nano carbon tube - metal | |
| CN105845462B (en) | Preparation method based on three-dimensional grapheme/mangano-manganic oxide combination electrode material | |
| Shriram et al. | Electrodeposition of nanocrystalline nickel—A brief review | |
| CN109137035A (en) | A kind of preparation method of aluminum-based copper-clad plate | |
| Wang et al. | Microstructural characteristic, outward-inward growth behavior and formation mechanism of MAO ceramic coating on the surface of ADC12 Al alloy with micro-groove | |
| CN103552312A (en) | Composite material with titanium diboride intermediate coating | |
| Wang et al. | Influence of treating frequency on microstructure and properties of Al2O3 coating on 304 stainless steel by cathodic plasma electrolytic deposition | |
| CN104499033A (en) | Preparation method of titanium diboride-titanium carbide composite thin film | |
| CN1962958A (en) | Method for preparing diamond-like film by liquid-phase electro-deposition technology | |
| Zhang et al. | A novel aqueous plasma electrolysis for carbon fiber | |
| CN101768760B (en) | TiB2-TiB/Ti gradient composite porous cathode material for aluminum electrolysis and preparation method thereof | |
| CN111394771B (en) | Method for preparing coating on surface of copper and copper alloy and copper product | |
| CN103436921A (en) | Method for forming aluminum-manganese-titanium alloy through electrodeposition of ionic liquid | |
| Lyu et al. | Efficient and clean manganese electrowinning in an anion-exchange membrane electrolyzer by pulse current electrodeposition method | |
| Chen et al. | Electrosynthesis and physicochemical properties of α–PbO2–CeO2–TiO2 composite electrodes | |
| CN1111212C (en) | Electrochemical deposition process to prepare hard film | |
| JP3554630B2 (en) | Electrolytic electrode with durability | |
| CN104480509A (en) | Titanium oxide film manufactured through plasma electrolysis deposition of organic aqueous solution system | |
| Wang et al. | Influence of Pt particles on the porosity of Al2O3 coating prepared by cathode plasma electrolytic deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130410 |