CN1227143A - Method for high energy pulse electric depositing of ceramic coating - Google Patents

Method for high energy pulse electric depositing of ceramic coating Download PDF

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CN1227143A
CN1227143A CN 98100569 CN98100569A CN1227143A CN 1227143 A CN1227143 A CN 1227143A CN 98100569 CN98100569 CN 98100569 CN 98100569 A CN98100569 A CN 98100569A CN 1227143 A CN1227143 A CN 1227143A
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moisture film
high energy
energy pulse
anode
ceramic coating
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CN1081093C (en
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于维平
何业东
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Beihang University
Beijing University of Aeronautics and Astronautics
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Beihang University
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Abstract

The present invention includes one high-energy pulse power source, water solution film applied to the surface of substrate and specific electrode structure. By utilizing the discharge energy of the high-energy pulse produced by the power source, the metal salt, ceramic sol-gel or nanometer-level ceramic grains inside the water solution film is deposited through reaction onto the surface of substrate to form ceramic coating. by means of the relative motion of the electrode and the substrate and different modes of applying water solution film to the surface of the substrate, various ceramic coatings, including heat-resisting, anticorrosive, wear-resisting and high-impedance ones, may be prepared on the surface of substrate.

Description

A kind of method of high energy pulse electric depositing of ceramic coating
The present invention is a kind of method of high energy pulse electric depositing of ceramic coating, and it mainly is the energy that utilizes the high energy pulse electricity to produce, and the substance reaction in the moisture film is deposited to substrate surface form one deck ceramic coating, and this method belongs to the sufacing field.
As everyone knows, ceramic coating plays an important role in science and technology and engineering, and ceramic coating can be divided into functional coating and structure coating two big classes by its effect.Functional coating then is to utilize coating material itself to make components and parts, for example, and the components and parts that utilize optical thin film, electric thin, optoelectronic thin-film, integrated optics film etc. to make.Structure coating then is at substrate surface deposition one deck ceramic coating, and it mainly acts on is in order to increase the service life of base material, makes base material become wear-resistant, corrosion-resistant, high temperature oxidation resisting, solar heat protection, protection against the tide and play certain beautifying and decorating effect.
At present, the method for preparing ceramic coating both at home and abroad has three kinds: physics method, chemical method and electrochemical process are arranged; Its physics method includes methods such as vacuum evaporation, magnetron sputtering, ion beam sputtering, molecule extension; Chemical method includes methods such as chemical vapour deposition (CVD), sol-gel process, liquid phase epitaxial method; Electrochemical process has electrochemical deposition method.The weak point that above-mentioned the whole bag of tricks exists is: the physical method great majority need expensive equipment and vacuum system.The ceramic coating that chemistry and electrochemical method are obtained is thinner, often need this ceramic coating is carried out sintering again, could improve its serviceability, methods such as thermal spraying, plasma spraying, detonation flame spraying are generally adopted in the preparation of thicker ceramic coating, but base material is subjected to serious heat affecting in spraying process, and is directed at base material distortion or damage.
The objective of the invention is to utilize energy that high energy electric pulse produces with the slaine in the moisture film, ceramic sol-gel or nanometer scale ceramics particle reactive deposition to metal base or non-metallic substrate surface, to obtain a kind of method of various ceramic coatings.The various ceramic coatings that adopt this method to obtain, it has heat-resisting, wear-resisting, corrosion-resistant and has performances such as high impedance.The present invention need not complicated vacuum system and control system, and equipment is simple, reduces cost.
A kind of method of high energy pulse electric depositing of ceramic coating, realize that this method must have a high energy pulse power supply, moisture film and the base material of inserting in the moisture film, this method is the high energy pulse discharge energy that utilizes the high energy pulse power supply to be produced, with the slaine in the moisture film, ceramic sol-gel or nanometer scale ceramics particle, reactive deposition is to the substrate surface that is placed in the moisture film, to form ceramic coating, the relative motion of electrode and base material by the high energy pulse power supply, and the mode that applies to substrate surface, can obtain various ceramic coatings in the substrate surface deposition, can prepare the function ceramics coating, also can prepare heat-resisting, corrosion-resistant, wear-resistant, the structural ceramics coating of high impedance.
Wherein, this base material can be metal base or non-metallic substrate, and the electrode of this high energy pulse power supply has three kinds of different mode of connection:
First kind of selected base material is metal base, the electrode mode of connection is: the negative electrode of high energy pulse power supply directly links to each other with metal base, apply the moisture film that thickness is 0.5-1mm on the surface of metal base, the anode of high energy pulse power supply is in the air, the air gap of anode and moisture film is 0.1-2mm, behind power connection, produce the high energy pulse discharge between anode and moisture film and the metal base, material in the moisture film is reacted deposit to metallic substrate surface, form ceramic coating in metallic substrate surface;
Second kind of selected base material is non-metallic substrate, the electrode mode of connection is: the negative electrode of high energy pulse power supply contacts with moisture film by metal or graphite, the anode of this cathode distance high energy pulse power supply is far away, when power connection, can not directly produce the high energy pulse discharge between anode and the negative electrode, but can produce high-energy discharge between anode and the moisture film, material in the moisture film is reacted deposit to the non-metallic substrate surface, form ceramic coating on the non-metallic substrate surface;
The third selected base material is a metal base, electrode connection mode is: the negative electrode of high energy pulse power supply 2 points that are connected in parallel simultaneously, any is that an end of negative electrode contacts with moisture film by metal or graphite, on the other hand the another end of negative electrode directly is connected with metal base, the anode of high capacity power source is far away apart from negative electrode, so, when power connection, can not directly discharge between anode and the negative electrode, but can produce high-energy discharge between anode and moisture film and the metal base, material in the moisture film is reacted deposit to metallic substrate surface, form ceramic coating in metallic substrate surface, this cycle is the initial stage of deposition of ceramic coatings, when complete one deck ceramic coating after metallic substrate surface forms, this metallic substrate surface then becomes the nonmetallic materials pottery, at this moment, the high energy pulse discharge mode changes over second kind of electrode johning knot mode, by producing high-energy discharge between anode and the moisture film, continue to make material in the moisture film to react and deposit to the surface of ceramic coating, make ceramic coating continue to thicken.
Wherein, the composition of this moisture film is by water be placed in the liquid that the mixture of slaine, ceramic sol-gel, nanometer scale ceramics particle or above-mentioned multiple material in the water is formed;
This slaine includes: nitrate, carbonate, oxalates, silicate, phosphate, borate etc.; This ceramic sol-gel includes: ceramic sol--gels such as silica sol-gel, zirconia sol-gel, alumina sol-gel;
This nanometer scale ceramics particle includes: various nanometer scale ceramics particles;
And the mixture of above-mentioned multiple material, change kind, content and ratio and can obtain various ceramic coatings.
Wherein, this moisture film can be static, flow or vibrate in the ultrasonic wave mode.This moisture film to the mode that applies of substrate surface can be: base material is placed in the water, by control water liquid level, has certain thickness moisture film at substrate surface; Can also adopt on base material and be coated with, drip, spill water membrane; Also can adopt the circulation moisture film, in base material pulsed discharge place spray water membrane, water film thickness is about 0.5-1mm.
Wherein, pulse voltage value between the negative electrode of this high energy pulse power supply and positive the two poles of the earth is 0.1kV-5kV, its waveform is a square wave, the size of this voltage depends primarily on the gap between anode and the moisture film, the critical voltage that the big more pulsing discharge in gap needs is high more, and the air gap is generally 0.5-3mm, and pulse frequency is 100-10000Hz, the duty ratio is 1: 1-1: 100, and the width of pulse is 1 μ s-10ms.
Advantage of the present invention is: equipment is simple, and technological process is simplified, the method flexible and convenient, and with low cost, city's field boundary competitiveness is strong, can be widely used in the science field of engineering technology.
The present invention has following accompanying drawing:
Fig. 1 is first kind of electrode mode of connection of the present invention.
Fig. 2 is second kind of electrode mode of connection of the present invention.
Fig. 3 is the third electrode mode of connection of the present invention.
Number in the figure is as follows:
1. base material 2. moisture films, 3. anodes (positive pole)
4. the 6. interface of moisture film and air of high energy pulse power supply 5. negative electrodes (negative pole)
7. base material 8. metals or graphite
Now enumerate specific embodiment and conjunction with figs. is described as follows:
The method of a kind of high energy pulse electric depositing of ceramic coating of the present invention sees also shown in Fig. 1,2,3, realizes that this method must have the cathode and anode 5 and 3 of a high energy pulse power supply 4, power supply, moisture film 2 and base material 1,7 etc.This high energy pulse power supply 4, its electrode 5,3 have three kinds of connected modes: first kind of electrode mode of connection (as shown in Figure 1), the base material of selecting for use 1 is metal base, the electrode mode of connection is: the negative electrode 5 of high energy pulse power supply 4 directly links to each other with metal base 1, applying thickness on the surface of metal base 1 is the moisture film 2 of 0.5-1mm, the anode 3 of high energy pulse power supply 4 is in the air, anode 3 is 0.1-2mm with the air gap of moisture film 2, behind power connection, produce the high energy pulse discharge between anode 3 and moisture film 2 and the metal base 1, material in the moisture film 2 is reacted deposit to metal base 1 surface, form ceramic coating in metallic substrate surface;
Second kind of electrode connection mode (as shown in Figure 2), the base material of selecting for use 7 is non-metallic substrate 7, the mode of connection of electrode is: the negative electrode 5 of high energy pulse power supply 4 contacts with moisture film 2 by metal or graphite 8, this negative electrode 5 is far away apart from the anode 3 of high energy pulse power supply, when power connection, can not directly produce the high energy pulse discharge between anode 3 and the negative electrode 5, but can produce high-energy discharge between anode 3 and the moisture film 2, material in the moisture film is reacted deposit to non-metallic substrate 7 surfaces, form ceramic coatings on non-metallic substrate 7 surfaces;
The third electrode connection mode (as shown in Figure 3), the base material of selecting for use 1 is metal base 1, electrode connection mode is: negative electrode 5 while and downlink connection 2 points of high energy pulse power supply 4, any is that an end of negative electrode 5 contacts with moisture film 2 by metal or graphite 8, on the other hand the another end of negative electrode 5 directly is connected with metal base 1, the anode 3 of high capacity power source 4 is far away apart from negative electrode 5, so, when power connection, can not directly discharge between anode 3 and the negative electrode 5, but can produce high-energy discharge between anode 3 and moisture film 2 and the metal base 1, material in the moisture film 2 is reacted deposit to metal base 1 surface, form ceramic coating on metal base 1 surface, this cycle is the initial stage of deposition of ceramic coatings, when complete one deck ceramic coating after metal base 1 surface forms, this metal base 1 surface then becomes the nonmetallic materials pottery, at this moment, the discharge mode of high energy pulse power supply 4 changes over second kind of electrode johning knot mode, by producing high-energy discharge between anode 3 and the moisture film 2, continue to make material in the moisture film 2 to react and deposit to the surface of ceramic coating, make ceramic coating continue to thicken.
Specific practice is as follows:
1. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 200Hz, is negative electrode with 1 chromium 18 nickel, 9 titaniums (1Cr18Ni9Ti) base material, is anode with the zirconium wire, and moisture film is 0.1M zirconium nitrate [Zr (NO 3) 4], the control thickness of liquid film is 0.5mm, and the air gap is 1mm, adopts the electrode structure of Fig. 1, and the discharge of moving anode continuous impulse obtains zirconia (ZrO 2) ceramic coating.
2. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 300Hz, is negative electrode with 1 chromium 18 nickel, 9 titaniums (1Cr18Ni9Ti) base material, is anode with the aluminum metal silk, and moisture film is 0.1M aluminum nitrate [Al (NO 3) 3], the control thickness of liquid film is 0.5mm, and the air gap is 1mm, adopts the electrode structure of Fig. 1, and the discharge of moving anode continuous impulse obtains aluminium oxide (Al 2O 3) ceramic coating.
3. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 400Hz, is negative electrode with the metal base, is anode with the zirconium wire, and moisture film is 0.1M chromic nitrate [Cr (NO 3) 3], the electrode structure of employing Fig. 1, the discharge of moving anode continuous impulse obtains chrome green (Cr 2O 3) ceramic membrane.
4. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 200Hz, is negative electrode with the metal base, is anode with the zirconium wire, and moisture film is the berkelium oxide (ZrO of 5 grams per liters 2) nano powder, the electrode structure of employing Fig. 1 obtains zirconia (ZrO after the discharge of moving anode continuous impulse 2) ceramic membrane.
5. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 200Hz, is negative electrode with the metal base, is anode with the zirconium wire, and moisture film is 0.1M zirconium nitrate [Zr (NO 3) 4] and the zirconia (ZrO of 5 grams per liters 2) nano powder, the electrode structure of employing Fig. 1 obtains zirconia (ZrO after the discharge of moving anode continuous impulse 2) ceramic membrane.
6. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 200Hz, is negative electrode with the metal base, with graphite is anode, moisture film is oxidation colloidal sol a--gel, adopts the electrode structure of Fig. 1, and the discharge of moving anode continuous impulse obtains silica (SiO 2) ceramic membrane.
7. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 200Hz, is negative electrode with 1 chromium 18 nickel, 9 titaniums (1Cr18Ni9Ti), is anode with metal berkelium silk, and moisture film is 0.09M zirconium nitrate [Zr (NO 3) 4The yttrium nitrate of]+O.01M [Y (NO 3) 3], the control thickness of liquid film is for O.5mm, and the air gap is 1mm, adopts the electrode structure of Fig. 1, and the moving anode continuous impulse discharges and obtains stabilized zirconia (ZrO 2)+yittrium oxide (Y 2O 3] ceramic coating.
8. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 200Hz, is negative electrode and anode with the metal zirconium silk, and base material is zirconia (ZrO 2) sheet, moisture film is 0.1M zirconium nitrate [Zr (NO 3) 4], the control thickness of liquid film is 0.5mm, and the air gap is 1mm, adopts the electrode structure of Fig. 2, and the discharge of moving anode continuous impulse obtains zirconia (ZrO 2) ceramic coating.
9. use the voltage pulse output of high energy pulse power supply to be 3kV, output frequency is 200Hz, is anode and negative electrode with the metal zirconium silk, and base material is 1 chromium 18 nickel, 9 titaniums (1Cr18Ni9Ti) sheet, and moisture film is zirconium nitrate [Zr (NO O.1M 3) 4], the control thickness of liquid film is 0.5mm, and the air gap is 1mm, adopts the electrode structure of Fig. 3, and the discharge of moving anode continuous impulse obtains thick zirconia (ZrO 2) ceramic coating.

Claims (5)

1. the method for a high energy pulse electric depositing of ceramic coating, realize that this method must have a high energy pulse power supply, moisture film and the base material of inserting in the moisture film, it is characterized in that: this method is the high energy pulse discharge energy that utilizes the high energy pulse power supply to be produced, with the slaine in the moisture film, ceramic sol-gel or nanometer scale ceramics particle, reactive deposition is to the substrate surface that is placed in the moisture film, to form ceramic coating, by the electrode of high energy pulse power supply and the relative motion that places the moisture film base material, and to the mode that applies moisture film of substrate surface, can obtain various ceramic coatings in the substrate surface deposition, can prepare the function ceramics coating, also can prepare heat-resisting, corrosion-resistant, wear-resistant, the structural ceramics coating of high impedance.
2. the method for a kind of high energy pulse electric depositing of ceramic coating according to claim 1, it is characterized in that: this base material can be metal base or non-metallic substrate, the electrode of this high energy pulse power supply has three kinds of different mode of connection;
First kind of selected base material is metal base, the electrode mode of connection is: the negative electrode of high energy pulse power supply directly links to each other with metal base, apply the moisture film that thickness is 0.5-1mm on the surface of metal base, the anode of high energy pulse power supply is in the air, the air gap of anode and moisture film is 0.1-2mm, behind power connection, produce the high energy pulse discharge between anode and moisture film and the metal base, material in the moisture film is reacted deposit to metallic substrate surface, form ceramic coating in metallic substrate surface;
Second kind of selected base material is non-metallic substrate, the electrode mode of connection is: the negative electrode of high energy pulse power supply contacts with moisture film by metal or graphite, the anode of this cathode distance high energy pulse power supply is far away, when power connection, can not directly produce the high energy pulse discharge between anode and the negative electrode, but can produce high-energy discharge between anode and the moisture film, material in the moisture film is reacted deposit to the non-metallic substrate surface, form ceramic coating at nonmetallic surface;
The third selected base material is a metal base, electrode connection mode is: the negative electrode of high energy pulse power supply 2 points that are connected in parallel simultaneously, any is that an end of negative electrode contacts with moisture film by metal or graphite, on the other hand the another end of negative electrode directly is connected with metal base, the anode of high capacity power source is far away apart from negative electrode, so, when power connection, can not directly discharge between anode and the negative electrode, but can produce high-energy discharge between anode and moisture film and the metal base, material in the moisture film is reacted deposit to metallic substrate surface, form ceramic coating in metallic substrate surface, this cycle is the initial stage of deposition of ceramic coatings, when complete one deck ceramic coating after metallic substrate surface forms, this metallic substrate surface then becomes the nonmetallic materials pottery, at this moment, the high energy pulse discharge mode changes over second kind of electrode johning knot mode, by producing high-energy discharge between anode and the moisture film, continue to make material in the moisture film to react and deposit to the surface of ceramic coating, make ceramic coating continue to thicken.
3. the method for a kind of high energy pulse electric depositing of ceramic coating according to claim 1 and 2 is characterized in that: the liquid that the composition of this moisture film is made up of water and the mixture that is placed in slaine, ceramic sol-gel, nanometer scale ceramics particle or above-mentioned multiple material in the water;
This slaine includes: nitrate, sulfate, oxalates, silicate, phosphate, borate etc.; This ceramic sol-gel includes: ceramic sol-gels such as silica sol-gel, berkelium oxide sol-gel, alumina sol-gel;
This nanometer scale ceramics particle includes: various nanometer scale ceramics particles;
And the mixture of above-mentioned multiple material, change kind, content and ratio and can obtain various ceramic coatings.
4. the method for a kind of high energy pulse electric depositing of ceramic coating according to claim 3, it is characterized in that: this moisture film can be static, flow or vibrate in the ultrasonic wave mode, this moisture film to the mode that applies of substrate surface can be: base material is placed in the moisture film, by control water liquid level, has certain thickness moisture film at substrate surface; Can also adopt on base material and be coated with, drip, spill water membrane; Also can adopt the circulation moisture film, in base material pulsed discharge place spray water membrane, water film thickness is about 0.5-1mm.
5. according to the method for claim 1 or 2 or 4 described a kind of high energy pulse electric depositing of ceramic coating, it is characterized in that: the pulse voltage value between the negative electrode of this high energy pulse power supply and positive the two poles of the earth is 0.1kV-5kV, its waveform is a square wave, the size of this voltage depends primarily on the gap between anode and the moisture film, the critical voltage that the big more pulsing discharge in gap needs is high more, the air gap is generally 0.5-3mm, pulse frequency is 100-10000Hz, the duty ratio is 1: 1-1: 100, and the width of pulse is 1 μ s-10ms.
CN98100569A 1998-02-24 1998-02-24 Method for high energy pulse electric depositing of ceramic coating Expired - Fee Related CN1081093C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104562128A (en) * 2015-01-09 2015-04-29 西安工业大学 Method for preparing thermal protection ceramic layer on surface of metal or metal composite material

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* Cited by examiner, † Cited by third party
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DE10357535A1 (en) * 2003-12-10 2005-07-07 Mtu Aero Engines Gmbh Ceramic material and method for repairing thermal barrier coatings with local damage
CN100469946C (en) * 2005-12-19 2009-03-18 广东工业大学 Preparation method of TiC ceramic coating

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ZA776047B (en) * 1977-10-11 1979-05-30 Essex Transducers Coating compositions,processes for depositing the same and articles resulting therefrom
SU1823534A1 (en) * 1990-11-20 1996-04-10 ПО "Чепецкий механический завод" Method to deposit ceramic coatings on zirconium and its alloys

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104562128A (en) * 2015-01-09 2015-04-29 西安工业大学 Method for preparing thermal protection ceramic layer on surface of metal or metal composite material

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