CN108315804B - Electrophoretic liquid for preparing manganous-manganic oxide coating and electrophoretic deposition process - Google Patents
Electrophoretic liquid for preparing manganous-manganic oxide coating and electrophoretic deposition process Download PDFInfo
- Publication number
- CN108315804B CN108315804B CN201810340908.5A CN201810340908A CN108315804B CN 108315804 B CN108315804 B CN 108315804B CN 201810340908 A CN201810340908 A CN 201810340908A CN 108315804 B CN108315804 B CN 108315804B
- Authority
- CN
- China
- Prior art keywords
- electrophoretic
- solution
- electrophoresis
- preparing
- sample
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
Abstract
The invention relates to the technical field of electrophoretic deposition, in particular to electrophoretic fluid for preparing a manganous-manganic oxide coating and an electrophoretic deposition process. Wet ball milling is carried out before the metal oxide particles are prepared into an electrophoretic solution, then, grinding is carried out twice by using a mortar, the treated solid particles and an additive are added into an organic solution for ultrasonic dispersion, and the particles fully adsorb protons and are positively charged and uniformly dispersed in the electrophoretic solution. The method has the advantages of simple process and low cost, and the obtained mangano-manganic oxide coating is uniform and flat, and the thickness can be accurately controlled by adjusting process parameters.
Description
Technical Field
The invention relates to the technical field of electrophoretic deposition, in particular to an electrophoretic solution for preparing a manganous-manganic oxide coating and an electrophoretic deposition process
Background
Solid Oxide Fuel Cells (SOFC) are a new generation of thermal energy conversion devices due to their characteristics of high conversion efficiency, low pollution, and diversified fuels. The choice of the linker directly affects the performance of the solid oxide fuel cell. In recent years, with the development of thin electrolyte layers and new electrode materials, SOFCs can be operated at temperatures below 800 ℃, and thus it has become possible to replace the conventional expensive lanthanum chromite-based ceramic materials with high-temperature oxidation resistant alloys as new interconnect materials. Ferritic stainless steel has the advantages of good oxidation resistance, low price, thermal expansion coefficient matching with SOFC and the like, and has been widely used as a metal connector material of SOFC cell stacks. But its application is severely limited by insufficient high-temperature oxidation resistance and cathode poisoning caused by Cr volatilization. The current solution to this problem is to try different methods to reduce the growth rate of the oxide film and to suppress Cr volatilization, and applying a protective coating on the surface of the metal connector not only improves the stability of the oxide film and compatibility with adjacent components, but also reduces the resistance of the oxide film on the surface of the alloy and suppresses Cr volatilization.
Currently, spinel coating materials are being investigated that exhibit suitable thermal matching with ferritic stainless steel substrates and other adjacent components (e.g., cathodes, anodes). The spinel coating material has excellent Cr matter absorbing capacity and can inhibit Cr poisoning of cathode caused by the volatilization of Cr-rich oxide layer to the surface layer. Among them, spinel coatings containing manganese have been widely studied due to their high electrical conductivity and large non-stoichiometric degree. Pure Mn3O4The coating has a thermal expansion coefficient which is more matched with that of ferritic stainless steel and lower resistance, does not contain Cr per se, is favorable for inhibiting the volatilization of Cr, and is a potential SOFC metal connector coating material.
The common preparation methods of the spinel coating mainly comprise a slurry coating method, a screen printing method, electroplating, electrophoretic deposition and the like. The electrophoretic deposition method can be carried out at normal temperature, residual thermal stress hardly exists between a deposition layer and a substrate, and the thickness of the film layer can be accurately controlled by adjusting process parameters, so that the electrophoretic deposition method is suitable for preparing the coating material. The method not only provides a unique visual angle in the aspect of controlling the microstructure and the thickness of the coating, but also can design a series of metal oxide coatings and can apply the coatings in the fields of corrosion, wear resistance, electrocatalysis and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides an electrophoretic solution for preparing a trimanganese tetroxide coating and an electrophoretic deposition process, discloses a preparation method of a trimanganese tetroxide electrophoretic suspension suitable for electrophoretic deposition and provides a process for preparing a deposited trimanganese tetroxide coating.
The specific technical scheme is as follows:
the electrophoresis liquid for preparing the manganous-manganic oxide coating comprises the following components in parts by weight:
125-500 mL of organic solvent
Manganic manganous oxide 5-40 g/L
0.3-3 g/L of additive
The preparation method comprises the following steps: firstly, carrying out wet ball milling on manganous-manganic oxide by using a ball mill, then, grinding by using a mortar, and repeatedly grinding twice to obtain Mn3O4Nanoparticles; mn after the above treatment3O4Adding the nanoparticles and the additive into an organic solution, and performing ultrasonic dispersion for 10-120 min to ensure that the particles fully adsorb protons with positive charges and are uniformly dispersed in the electrophoretic solution.
The organic solvent is one or more of methanol, ethanol, isopropanol, acetone and acetylacetone.
The additive is one or more of hydrochloric acid, iodine, acetic acid, magnesium chloride and nitric acid.
The electrophoretic deposition process for preparing the manganous-manganic oxide coating comprises the following steps:
(1) pretreatment of substrates
Mechanically polishing and leveling the matrix by using abrasive paper, and then placing the matrix in an ultrasonic position in an oil removing agentConditioning for 5-30 min, and then immersing the sample in 5-20% Na at 40-60 DEG C2CO3Alkali washing is carried out for 5-15 min in the solution, and the sample after oil removal treatment is placed in 5-15% H2SO4Slightly stirring the solution for 10-60 s, and pre-plating a thin layer of pre-plated metal on the surface of the substrate;
(2) preparation of electrophoretic suspensions
Firstly, carrying out wet ball milling on manganous-manganic oxide by using a ball mill, wherein the rotating speed of the ball mill is 300-500 rpm, and the alcohol-material ratio is 0.8: 1-1.2: 1, ball-to-material ratio of 10: 1-20: 1, ball milling time is 2-12 h, grinding with a mortar, and repeating twice to obtain Mn3O4Nanoparticles; mn after the above treatment3O4Adding the nano particles and the additive into the organic solution and carrying out ultrasonic dispersion for 10-120 min;
(3) electrophoretic deposition of Mn3O4Formula of electrophoresis liquid and electrophoresis process
Temperature of the electrophoretic fluid: 30-50 ℃, current density: 0.75 to 5mA/cm2And electrophoresis time: 5 to 300 seconds.
The substrate is one of stainless steel, iron sheet and conductive glass.
The pre-plated metal is one of nickel, copper and cobalt.
The thickness of the pre-plated metal is 0.3-3 mu m.
The oil removing agent is one of ethanol, diethyl ether and acetone.
Compared with the prior art, the invention has the following beneficial technical effects:
by utilizing the electrophoretic solution formula and the electrophoretic deposition process provided by the invention, an electrophoretic deposition layer with a uniform and flat surface can be obtained, and the deposition layer can be characterized. The surface appearance of the sample is observed through a Scanning Electron Microscope (SEM), and smooth and uniform Mn can be seen3O4The particles are distributed on the substrate. The phase structure of the deposited layer was analyzed by X-ray diffractometry (XRD), and it was found that the coating was mainly composed of Mn3O4And (4) forming.
The invention takes manganous-manganic oxide as raw material, repeatedly ball-milling the raw material at room temperature to obtain nanometer manganous-manganic oxide nanometer particles3O4The nano particles are small in size and concentrated in particle size distribution, and good conditions are provided for the next suspension preparation and the subsequent electrophoretic deposition. In the pretreatment of the substrate, a thin layer of pre-plated metal is electroplated on the surface of the substrate, so that the binding force of a subsequent electrophoretic deposition layer is better. The preparation method of the electrophoresis suspension liquid comprises the step of adding manganous-manganic oxide and an additive into an organic solution for ultrasonic dispersion, wherein the additive has the capability of reacting with the organic solution to obtain hydrogen protons, so that manganous-manganic oxide particles adsorb the hydrogen protons and are positively charged, and uniform and stable suspension liquid is further obtained. The method has the advantages of simple process and low cost, and the obtained mangano-manganic oxide coating is uniform and flat, has the thickness accurately controlled by adjusting process parameters, and is easy for industrial production.
Drawings
FIG. 1 Mn deposited in example 53O4Surface topography (SEM) images of the coatings;
FIG. 2 Mn deposited in example 53O4Phase structure analysis (XRD) spectrum of the coating;
FIG. 3 Mn deposited in example 53O4And (4) performing section element line scanning analysis on the coating.
Detailed Description
The invention is described in detail below with reference to the drawings and specific embodiments, but the scope of the invention is not limited by the drawings and the embodiments.
Example 1:
1. pretreatment of substrates
The substrate used in this example was stainless steel and had dimensions of 15 mm. times.10 mm. times.2 mm. The matrix is subjected to polishing, oil removal, descaling, water washing, drying and other treatment. The invention uses water abrasive sand paper to mechanically polish and level the matrix, and takes 240#, 400#, 600#, 800#, 1000# and 2000# sand paper to polish in sequence. And then deoiling, namely deoiling by adopting anhydrous acetone, putting the sample into a beaker containing acetone, carrying out ultrasonic treatment for 5min, and finally taking out and air-drying. The sample was then immersed in 5% Na at 60 deg.C2CO3And (5) carrying out alkali washing in the solution for 5min, taking out, repeatedly washing with deionized water, and drying. Samples after degreasing were immersed in 15% H2SO4And (4) slightly stirring the solution for 20s, taking out the solution, repeatedly washing the solution by using deionized water until no stripes exist, drying the solution, and sealing the solution for standby. And finally, pre-plating a thin layer of copper on the sample to ensure that the binding force of the subsequent electrophoretic deposition layer is better.
2. Preparation of electrophoretic suspensions
Because the powder particles are fine and not easy to wet, the powder particles float on the surface of the electrophoretic liquid when the electrophoretic liquid is added, most of the powder particles are agglomerated and deposited at the bottom of a beaker, and suspension liquid with uniformly distributed particles is difficult to form, therefore, the pretreatment of the particles is particularly important for the configuration of the electrophoretic suspension liquid, and the method comprises the following steps: (1) firstly, carrying out wet ball milling on manganous-manganic oxide by using a ball mill, wherein the rotating speed of the ball mill is 400rpm, and the alcohol-material ratio is 0.8: 1, ball milling for 5 hours at a ball-to-material ratio of 20:1, then grinding with a mortar, and repeating twice to obtain Mn3O4 nanoparticles; (2) and adding the treated Mn3O4 nano particles and additives into an organic solution and performing ultrasonic dispersion for 60min, so that the powder fully adsorbs protons to be positively charged and is uniformly dispersed in the electrophoretic solution.
3. The formula and the electrophoresis process of the electrophoretic deposition Mn3O4 electrophoresis liquid are as follows:
the electrophoretic deposition operation method comprises the following steps: firstly, placing an electrophoresis tank in a water bath, heating to a preset temperature, clamping a to-be-electrophoresed stainless steel sample subjected to polishing, oil removal, acid washing activation and other treatment by using tweezers, fixing the sample on an electrode frame, immersing the sample in an electrophoresis solution, connecting a lead, turning on an electrophoresis power supply, adjusting the current to a set value, carrying out constant-current electrophoretic deposition, turning off the power supply after a specified time is reached, removing the lead, and taking out the sample for natural air drying.
Example 2:
1. pretreatment of substrates
The substrate used in this example was a conductive glass having dimensions of 15mm by 10mm by 2 mm. The matrix is subjected to polishing, oil removal, descaling, water washing, drying and other treatment. The invention uses water abrasive paper to mechanically polish and level the matrix, and takes 240#, 400#, 600#, 80 # in sequenceAnd (5) polishing with 0#, 1000#, 2000# sandpaper. And then deoiling, namely deoiling by adopting anhydrous acetone, putting the sample into a beaker containing acetone, carrying out ultrasonic treatment for 30min, and finally taking out and air-drying. The sample was then immersed in 20% Na at 50 deg.C2CO3And (4) carrying out alkali washing in the solution for 10min, taking out, repeatedly washing with deionized water, and drying. The samples after degreasing were immersed in 10% H2SO4And (4) slightly stirring the solution for 10s, taking out the solution, repeatedly washing the solution by using deionized water until no stripes exist, drying the solution, and sealing the solution for standby. And finally, pre-plating a thin layer of copper on the sample to ensure that the binding force of the subsequent electrophoretic deposition layer is better.
2. Preparation of electrophoretic suspensions
Because the powder particles are fine and not easy to wet, the powder particles float on the surface of the electrophoretic liquid when the electrophoretic liquid is added, most of the powder particles are agglomerated and deposited at the bottom of a beaker, and suspension liquid with uniformly distributed particles is difficult to form, therefore, the pretreatment of the particles is particularly important for the configuration of the electrophoretic suspension liquid, and the method comprises the following steps: (1) firstly, carrying out wet ball milling on manganous manganic oxide by using a ball mill, wherein the rotating speed of the ball mill is 300rpm, the alcohol-material ratio is 1.2:1, and the ball-material ratio is 15: 1, ball milling for 2 hours, grinding by using a mortar, and repeating twice to obtain Mn3O4Nanoparticles; (2) mn after treatment3O4Adding the nano particles and the additive into the organic solution and carrying out ultrasonic dispersion for 10min, so that the powder fully adsorbs protons with positive charge and is uniformly dispersed in the electrophoretic solution.
3. The formula and the electrophoresis process of the electrophoretic deposition Mn3O4 electrophoresis liquid are as follows:
the electrophoretic deposition operation method comprises the following steps: firstly, placing an electrophoresis tank in a water bath, heating to a preset temperature, clamping a to-be-electrophoresed stainless steel sample subjected to polishing, oil removal, acid washing activation and other treatment by using tweezers, fixing the sample on an electrode frame, immersing the sample in an electrophoresis solution, connecting a lead, turning on an electrophoresis power supply, adjusting the current to a set value, carrying out constant-current electrophoretic deposition, turning off the power supply after a specified time is reached, removing the lead, and taking out the sample for natural air drying.
Example 3:
1. pretreatment of substrates
The substrate used in this example was an iron plate having dimensions of 15 mm. times.10 mm. times.2 mm. The matrix is subjected to polishing, oil removal, descaling, water washing, drying and other treatment. The invention uses water abrasive sand paper to mechanically polish and level the matrix, and takes 240#, 400#, 600#, 800#, 1000# and 2000# sand paper to polish in sequence. And then deoiling, namely deoiling by adopting absolute ethyl alcohol, putting the sample into a beaker containing the ethyl alcohol, carrying out ultrasonic treatment for 10min, and finally taking out and air-drying. The sample was then immersed in 10% Na at 60 deg.C2CO3And (5) carrying out alkali washing in the solution for 5min, taking out, repeatedly washing with deionized water, and drying. The samples after degreasing were immersed in 5% H2SO4And (4) slightly stirring the solution for 60s, taking out the solution, repeatedly washing the solution by using deionized water until no stripes exist, drying the solution, and sealing the solution for standby. And finally, pre-plating a thin layer of nickel on the sample to ensure that the binding force of the subsequent electrophoretic deposition layer is better.
2. Preparation of electrophoretic suspensions
Because the powder particles are fine and not easy to wet, the powder particles float on the surface of the electrophoretic liquid when the electrophoretic liquid is added, most of the powder particles are agglomerated and deposited at the bottom of a beaker, and suspension liquid with uniformly distributed particles is difficult to form, therefore, the pretreatment of the particles is particularly important for the configuration of the electrophoretic suspension liquid, and the method comprises the following steps: (1) firstly, carrying out wet ball milling on manganous-manganic oxide by using a ball mill, wherein the rotating speed of the ball mill is 400rpm, the alcohol-material ratio is 1.2:1, and the ball-material ratio is 10: 1, ball milling for 10 hours, grinding by using a mortar, and repeating twice to obtain Mn3O4Nanoparticles; (2) mn after treatment3O4Adding the nano particles and the additive into the organic solution and carrying out ultrasonic dispersion for 30min, so that the powder fully adsorbs protons with positive charge and is uniformly dispersed in the electrophoretic solution.
3. Electrophoretic deposition of Mn3O4The formula and the electrophoresis process of the electrophoresis liquid are as follows:
the electrophoretic deposition operation method comprises the following steps: firstly, placing an electrophoresis tank in a water bath, heating to a preset temperature, clamping a to-be-electrophoresed stainless steel sample subjected to polishing, oil removal, acid washing activation and other treatment by using tweezers, fixing the sample on an electrode frame, immersing the sample in an electrophoresis solution, connecting a lead, turning on an electrophoresis power supply, adjusting the current to a set value, carrying out constant-current electrophoretic deposition, turning off the power supply after a specified time is reached, removing the lead, and taking out the sample for natural air drying.
Example 4:
1. pretreatment of substrates
The substrate used in this example was an iron plate having dimensions of 15 mm. times.10 mm. times.2 mm. The matrix is subjected to polishing, oil removal, descaling, water washing, drying and other treatment. The invention uses water abrasive sand paper to mechanically polish and level the matrix, and takes 240#, 400#, 600#, 800#, 1000# and 2000# sand paper to polish in sequence. And then deoiling, namely deoiling by adopting absolute ethyl alcohol, putting the sample into a beaker containing the ethyl alcohol, carrying out ultrasonic treatment for 10min, and finally taking out and air-drying. The sample was then immersed in 20% Na at 40 deg.C2CO3Washing with alkali in the solution for 15min, taking out, repeatedly washing with deionized water, and blow-drying. The samples after degreasing were immersed in 10% H2SO4And (4) slightly stirring the solution for 30s, taking out the solution, repeatedly washing the solution by using deionized water until no stripes exist, drying the solution, and sealing the solution for standby. And finally, pre-plating a thin layer of cobalt on the sample to ensure that the binding force of the subsequent electrophoretic deposition layer is better.
2. Preparation of electrophoretic suspensions
Because the powder particles are fine and not easy to wet, the powder particles float on the surface of the electrophoretic liquid when the electrophoretic liquid is added, most of the powder particles are agglomerated and deposited at the bottom of a beaker, and suspension liquid with uniformly distributed particles is difficult to form, therefore, the pretreatment of the particles is particularly important for the configuration of the electrophoretic suspension liquid, and the method comprises the following steps: (1) firstly, carrying out wet ball milling on manganous-manganic oxide by using a ball mill, wherein the rotating speed of the ball mill is 500rpm, and the alcohol-material ratio is 0.8: 1, ball material ratio of 10: 1, ball milling for 12 hours, grinding by using a mortar, and repeating twice to obtain Mn3O4 nanoparticles; (2) mn after treatment3O4Adding the nanoparticles and additives into organic solution, and ultrasonically dispersing for 120min to make the powder fully adsorb proton bandPositively charged and uniformly dispersed in the electrophoretic fluid.
3. Electrophoretic deposition of Mn3O4The formula and the electrophoresis process of the electrophoresis liquid are as follows:
the electrophoretic deposition operation method comprises the following steps: firstly, placing an electrophoresis tank in a water bath, heating to a preset temperature, clamping a to-be-electrophoresed stainless steel sample subjected to polishing, oil removal, acid washing activation and other treatment by using tweezers, fixing the sample on an electrode frame, immersing the sample in an electrophoresis solution, connecting a lead, turning on an electrophoresis power supply, adjusting the current to a set value, carrying out constant-current electrophoretic deposition, turning off the power supply after a specified time is reached, removing the lead, and taking out the sample for natural air drying.
Example 5:
1. pretreatment of substrates
The substrate used in this example was stainless steel and had dimensions of 15 mm. times.10 mm. times.2 mm. The matrix is subjected to polishing, oil removal, descaling, water washing, drying and other treatment. The invention uses water abrasive sand paper to mechanically polish and level the matrix, and takes 240#, 400#, 600#, 800#, 1000# and 2000# sand paper to polish in sequence. Then deoiling, deoiling by adopting anhydrous ether, putting the sample in a beaker containing ether, carrying out ultrasonic treatment for 20min, and finally taking out and air-drying. The sample was then immersed in 10% Na at 50 deg.C2CO3And (4) carrying out alkali washing in the solution for 10min, taking out, repeatedly washing with deionized water, and drying. The samples after degreasing were immersed in 10% H2SO4And (4) slightly stirring the solution for 40s, taking out the solution, repeatedly washing the solution by using deionized water until no stripes exist, drying the solution, and sealing the solution for standby. And finally, pre-plating a thin layer of nickel on the sample to ensure that the binding force of the subsequent electrophoretic deposition layer is better.
2. Preparation of electrophoretic suspensions
Because the powder particles are fine and difficult to wet, the powder particles float on the surface of the electrophoretic solution when the electrophoretic solution is added, most of the powder particles are agglomerated and deposited at the bottom of the beaker, and suspension with uniformly distributed particles is difficult to form, the pretreatment of the particles is particularly important for the configuration of the electrophoretic suspension, and the pretreatment is particularly important for the configuration of the electrophoretic suspensionThe method comprises the following steps: (1) firstly, carrying out wet ball milling on manganous manganic oxide by using a ball mill, wherein the rotating speed of the ball mill is 500rpm, the alcohol-material ratio is 1:1, and the ball-material ratio is 15: 1, ball milling for 10 hours, grinding by using a mortar, and repeating twice to obtain Mn3O4Nanoparticles; (2) mn after treatment3O4Adding the nano particles and additives into the organic solution and carrying out ultrasonic dispersion for 50min, so that the powder fully adsorbs protons with positive charge and is uniformly dispersed in the electrophoretic solution.
3. Electrophoretic deposition of Mn3O4The formula and the electrophoresis process of the electrophoresis liquid are as follows:
the electrophoretic deposition operation method comprises the following steps: firstly, placing an electrophoresis tank in a water bath, heating to a preset temperature, clamping a to-be-electrophoresed stainless steel sample subjected to polishing, oil removal, acid washing activation and other treatment by using tweezers, fixing the sample on an electrode frame, immersing the sample in an electrophoresis solution, connecting a lead, turning on an electrophoresis power supply, adjusting the current to a set value, carrying out constant-current electrophoretic deposition, turning off the power supply after a specified time is reached, removing the lead, and taking out the sample for natural air drying.
FIG. 1 Mn deposited in example 53O4Surface topography (SEM) of the coating, FIG. 2 is Mn deposited in example 53O4Phase structure analysis (XRD) spectrum of the coating, FIG. 3 is Mn deposited in example 53O4And (4) performing section element line scanning analysis on the coating. As can be seen from the figure, Mn can be seen in FIG. 13O4The particles are uniformly deposited on the surface of the substrate, and FIG. 2 shows well Ni and Mn3O4The peak intensity of Ni is, as expected, significantly lower than that of the other phases, due to the shorter pre-plating time, only a thin layer of Ni is present, and also due to the thinner coating, X-rays can pass through the coating to reach the substrate, so that Fe-Cr phase in the substrate is still present. FIG. 3 shows that the substrate has good adhesion to the coating, which consists mainly of an inner thin Ni layer and an outer Mn layer3O4Layer composition, the thickness of the coating is approximately 4 μm or so. Thus, it is possible to provideThe trimanganese tetroxide coating can be successfully deposited on the substrate by an electrophoresis method.
Claims (7)
1. An electrophoretic fluid for preparing a mangano-manganic oxide coating is characterized in that: the electrophoresis liquid comprises the following components in percentage by weight:
125-500 mL of organic solvent
Manganic manganous oxide 5-40 g/L
0.3-3 g/L of additive
The preparation method comprises the following steps: firstly, carrying out wet ball milling on manganous-manganic oxide by using a ball mill, then, grinding by using a mortar, and repeatedly grinding twice to obtain Mn3O4Nanoparticles; mn after the above treatment3O4Adding the nano particles and additives into an organic solution, and performing ultrasonic dispersion for 10-120 min to ensure that the particles fully adsorb protons with positive charges and are uniformly dispersed in an electrophoresis solution; the additive is one or more of hydrochloric acid, iodine, acetic acid, magnesium chloride and nitric acid.
2. The electrophoretic fluid for preparing a trimanganese tetroxide coating according to claim 1, wherein: the organic solvent is one or more of methanol, ethanol, isopropanol, acetone and acetylacetone.
3. The electrophoresis process for preparing a trimanganese tetroxide coating by using the electrophoresis solution for preparing a trimanganese tetroxide coating according to claim 1, wherein the electrophoresis process comprises the following steps:
(1) pretreatment of substrates
Mechanically polishing and leveling the matrix by using water-milled sand paper, then placing the matrix in an oil removing agent for ultrasonic treatment for 5-30 min, and then soaking a sample in 5-20% Na at 40-60 DEG C2CO3Alkali washing is carried out for 5-15 min in the solution, and the sample after oil removal treatment is placed in 5-15% of H2SO4Slightly stirring the solution for 10-60 s, and pre-plating a thin layer of pre-plated metal on the surface of the substrate;
(2) preparation of electrophoretic suspensions
Firstly, the tetraoxide is oxidizedPerforming wet ball milling on manganese by using a ball mill, wherein the rotating speed of the ball mill is 300-500 rpm, and the alcohol-material ratio is 0.8: 1-1.2: 1, ball-to-material ratio of 10: 1-20: 1, ball milling time is 2-12 h, grinding with a mortar, and repeating twice to obtain Mn3O4Nanoparticles; mn after the above treatment3O4Adding the nano particles and the additive into the organic solution and carrying out ultrasonic dispersion for 10-120 min;
(3) electrophoretic deposition of Mn3O4Formula of electrophoresis liquid and electrophoresis process
Temperature of the electrophoretic fluid: 30-50 ℃, current density: 0.75 to 5mA/cm2And electrophoresis time: 5 to 300 seconds.
4. The electrophoretic process for preparing a trimanganese tetroxide coating according to claim 3, wherein: the substrate is one of stainless steel, iron sheet and conductive glass.
5. The electrophoretic process for preparing a trimanganese tetroxide coating according to claim 3, wherein: the pre-plated metal is one of nickel, copper and cobalt.
6. The electrophoretic process for preparing a trimanganese tetroxide coating according to claim 3, wherein: the thickness of the pre-plated metal is 0.3-3 mu m.
7. The electrophoretic process for preparing a trimanganese tetroxide coating according to claim 3, wherein: the oil removing agent is one of ethanol, diethyl ether and acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810340908.5A CN108315804B (en) | 2018-04-17 | 2018-04-17 | Electrophoretic liquid for preparing manganous-manganic oxide coating and electrophoretic deposition process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810340908.5A CN108315804B (en) | 2018-04-17 | 2018-04-17 | Electrophoretic liquid for preparing manganous-manganic oxide coating and electrophoretic deposition process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108315804A CN108315804A (en) | 2018-07-24 |
| CN108315804B true CN108315804B (en) | 2020-12-25 |
Family
ID=62898570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810340908.5A Active CN108315804B (en) | 2018-04-17 | 2018-04-17 | Electrophoretic liquid for preparing manganous-manganic oxide coating and electrophoretic deposition process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108315804B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032600A (en) * | 2021-11-12 | 2022-02-11 | 重庆大学 | Preparation method of Al/NiO energetic film based on electrophoretic deposition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7828619B1 (en) * | 2005-08-05 | 2010-11-09 | Mytitek, Inc. | Method for preparing a nanostructured composite electrode through electrophoretic deposition and a product prepared thereby |
| CN104499012B (en) * | 2015-01-14 | 2018-02-13 | 东北大学 | A kind of alkaline copper-based composite plating bath and electroplating technology |
| US9923189B2 (en) * | 2016-02-02 | 2018-03-20 | GM Global Technology Operations LLC | Electrophoretic deposition of an electrode for a lithium-based battery |
| CN107527744A (en) * | 2016-06-22 | 2017-12-29 | 广州墨羲科技有限公司 | Graphene-nano particle-nano-sized carbon wall composite, its manufacture method and application |
-
2018
- 2018-04-17 CN CN201810340908.5A patent/CN108315804B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108315804A (en) | 2018-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105734606B (en) | A kind of SPE water electrolysis structure of ultra-thin membrane electrode and its preparation and application | |
| Wang et al. | In situ coating of a continuous mesoporous bimetallic PtRu film on Ni foam: a nanoarchitectured self-standing all-metal mesoporous electrode | |
| Zhang et al. | Sb-doped SnO2 nanoparticle-modified carbon paper as a superior electrode for a vanadium redox flow battery | |
| Mohammadi et al. | Characterization of PbO2 coating electrodeposited onto stainless steel 316L substrate for using as PEMFC's bipolar plates | |
| Fu et al. | In-situ chemical conversion film for stabilizing zinc metal anodes | |
| Nikiforidis et al. | Indium modified graphite electrodes on highly zinc containing methanesulfonate electrolyte for zinc-cerium redox flow battery | |
| Wang et al. | Facile synthesis MnCo2O4. 5@ C nanospheres modifying PbO2 energy-saving electrode for zinc electrowinning | |
| Ouyan et al. | Physical and Electrochemical Properties of Ni-P/TiN coated Ti for bipolar plates in PEMFCs | |
| CN108315804B (en) | Electrophoretic liquid for preparing manganous-manganic oxide coating and electrophoretic deposition process | |
| Liu et al. | Novel hybrid coating of TiN and carbon with improved corrosion resistance for bipolar plates of PEM water electrolysis | |
| Yu et al. | Electrodeposition of MnO2-doped Pb-0.6% Sb/α-PbO2/β-PbO2 novel composite energy-saving anode for zinc electrowinning | |
| Yu et al. | Comparison of novel composite anodes with different proportions of α/β-PbO2 and the application in long-period zinc electrowinning | |
| Zhang et al. | Modification and durability of carbon paper gas diffusion layer in proton exchange membrane fuel cell | |
| CN117117228A (en) | Fuel cell metal bipolar plate and fuel cell | |
| CN113328111B (en) | Stainless steel bipolar plate with chromium-based nitride composite coating and preparation method thereof | |
| CN107794556B (en) | A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates | |
| CN109888304A (en) | A kind of preparation method of membrane electrode, preparation method and a kind of fuel cell and fuel cell | |
| CN114045509B (en) | Seawater electrolysis device with sodium ion conduction and application thereof | |
| CN113584517A (en) | Preparation method of non-noble metal Ni-Mo-P-B efficient electro-catalytic hydrogen evolution electrode | |
| CN109052574B (en) | Preparation of Ti/SnO based on tricarboxylic organic acid-Sn (II)/Sb (III) complex2Method for producing Sb electrode | |
| CN110931264B (en) | Iron in-situ doped sodium titanate electrode material and preparation method thereof | |
| Wang et al. | Effect of Cl−/Mn2+ ions on the oxygen evolution and corrosion behaviors of 3D-Pb-Ca-Sn anode for copper electrowinning | |
| CN112221892A (en) | Novel metal bipolar plate surface modification method | |
| CN112342577A (en) | Method for preparing cobalt-manganese spinel coating | |
| CN112609210A (en) | CeO (CeO)2Cu/Mn-doped composite film/microcrystalline interface layer and metal-based composite connector and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |