CN114921759A - Multi-arc ion plating coating process - Google Patents
Multi-arc ion plating coating process Download PDFInfo
- Publication number
- CN114921759A CN114921759A CN202210539640.4A CN202210539640A CN114921759A CN 114921759 A CN114921759 A CN 114921759A CN 202210539640 A CN202210539640 A CN 202210539640A CN 114921759 A CN114921759 A CN 114921759A
- Authority
- CN
- China
- Prior art keywords
- coating
- target
- ion plating
- arc ion
- arc
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/22—Moulds for peculiarly-shaped castings
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0664—Carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a multi-arc ion plating coating process. The process comprises the following steps: step 1, base material pretreatment; step 2, magnetically controlling the multi-arc ion plating of the TiN transition coating; step 3, carrying out magnetic control multi-arc ion plating on the TiTaN coating; and 4, magnetically controlling the multi-arc ion plating of the TiTaN-BiScCoCN coating. The base material is etched by glow discharge and ion bombardment, so that the bonding strength of the coating and the base material is improved, meanwhile, the base material is subjected to multi-arc ion plating of a TiTaN-BiScCoCN coating by a magnetic control arc technology, a TaTi target is used as a target material for secondary coating, a Co target material and a BiScC target are used in tertiary coating, so that the coating is better bonded, and the compactness and the wear resistance of the coating are improved. Compared with the prior art, the TiTaN-BiScCoCN coating prepared by the multi-arc ion plating coating process has the advantages of good wear resistance, good hot salt corrosion resistance and good bonding strength with a substrate.
Description
Technical Field
The invention relates to the technical field of surface protective coatings, in particular to a multi-arc ion plating coating process.
Background
The surface technology of materials can be roughly classified into surface coating, surface modification technology and thin film technology in the subject. The specific process comprises the following steps: electroplating, coating, build-up welding and hot sprayingThermal diffusion, chemical conversion, vapor deposition, three-beam modification, and the like. The film forming techniques in the thin film technology are classified into two types, which are more representative at present: the physical vapor deposition technology and the chemical vapor deposition technology are that atoms of one or more special materials are transferred to the surface of another material through a complex physical or chemical method, so that the materials with special functions are combined with the surface material of the object to be optimized, and the surface of the object to be optimized obtains special properties, such as higher hardness, lower friction coefficient, smaller surface roughness and the like. Chemical vapor deposition, that is, a chemical principle is utilized to enable a material with special performance to participate in a specific chemical reaction in a gasification state, a solid substance generated by the reaction is deposited on the surface of a substrate, and a film layer with special performance is finally formed on the surface of the substrate. The high temperature easily causes the metallographic structure change on the surface of the matrix, and influences the purity and stability of the film. Physical vapor deposition techniques can be broadly classified into three types, vacuum evaporation, sputtering, and ion plating. The vacuum evaporation plating is to deposit a solid target material on the surface of a substrate after evaporating or vaporizing the solid target material at a high temperature by using heating methods such as resistance, laser or induction heating to form a film layer, but the uniformity of the deposited film is poor, and the bonding force between the deposited film and the substrate is low; the sputtering plating is to utilize high-energy inert gas ions to impact the surface of a target under the action of an electric field, a magnetic field or a composite field, energy is transferred and lost in the high-energy collision process, a large amount of target ions or ion clusters which are separated from the surface of the target and a large amount of heat are generated,however, the device is not limited to the specific type of the deviceThen, the film is deposited on the surface of a substrate to form a film under the action of a specific physical transmission field, but the practical application of the traditional sputtering coating is limited due to the high working air pressure and the low deposition speed; the ion plating is to deposit ions on the surface of a target material to the surface of a substrate under the action of a strong electric field to form a thin film according to the principles of glow discharge or arc discharge, wherein the multi-arc ion plating technology in the arc type ion plating is one of the mainstream technologies in the current industrial production.
The multi-arc ion plating combines the characteristics of vacuum evaporation and sputtering coating, a coating material is used as a target cathode, a plasma area is formed by utilizing vacuum arc discharge, target particles evaporated by the arc discharge move to the plasma area and then are ionized, and charged target particles accelerate to move to the surface of a substrate under the drive of negative bias voltage and then are deposited to form a film. The most remarkable characteristic of the multi-arc ion plating is that a molten pool is not needed, plasma can be directly generated from a cathode, cathode targets can be freely distributed according to the shape of a workpiece, and multi-arc ion plating equipment is greatly simplified. Meanwhile, the ionization-excited particles have high energy, so that the prepared film has high density, good strength and durability and good bonding strength between film layers. However, the problems of unstable arc spot movement and droplet splashing in the deposition process caused by the imperfection of the arc control technology in the arc ion plating technology have not been solved effectively. Researchers try to limit the arc spot movement by using modes of shielding electric arcs, filtering electric arcs and the like, or influence the arc spot movement by changing an electric arc power supply, an arc striking mode, an arc control magnetic field and the like, but the effect is not ideal. During this time, it was recognized that the most effective way to control arc was magnetic field arc control, which controlled the arc spot motion in a manner that adjusted the magnitude of the magnetic field based on the motion state of the arc spot. At present, researches on various aspects of magnetic fields, arc spots and targets, including arc flow, bias voltage, atmosphere and the like, are gradually carried out. After certain development, the multi-arc ion plating is practically applied to numerous industries such as catering utensils, sanitary wares, industrial decoration, hardware tools, automobile and motorcycle light industry, medical appliances, aerospace, military mechanical equipment and the like. In order to meet the field quality requirements, the requirements on multi-arc ion plating coatings are higher and higher. The coating is developed in two directions of preparing a multi-element mixed coating by composite deposition of two or more materials and preparing a multilayer structure by selecting different film materials, researchers prepare a (Ti, Cr) N mixed coating, and find that the mechanical property and the corrosion resistance of the (Ti, Cr) N mixed coating are superior to those of a single film coating. More researchers dope Al element to prepare the (Ti, Ag, Cr) N mixed coating, and the coating performance is improved. Therefore, the multi-element coating is a research hotspot.
The invention patent with publication number CN104018133B discloses a process for preparing a multilayer composite protective coating on the surface of a sintered neodymium-iron-boron magnet by multi-arc ion plating, which comprises the steps of cleaning the surface of the sintered neodymium-iron-boron magnet, removing oil and rust on the surface of the magnet, cleaning the surface by glow discharge back sputtering in a vacuum coating chamber, plating Ti or Cr on the surface by using multi-arc ions as a transition layer, plating Al or Al alloy on the surface by using the multi-arc ions, and finally plating an AlN layer on the surface by using the multi-arc ions to obtain the multilayer composite protective coating. The transition layer, the corrosion-resistant layer and the surface barrier and wear-resistant layer composite protective coating are efficiently prepared on the surface of the sintered neodymium-iron-boron magnet by adopting a multi-arc ion plating deposition technology, so that the corrosion resistance of the sintered neodymium-iron-boron magnet is remarkably improved, and the service life is prolonged. In the invention, the AlN of the outer layer of the composite coating is formed by gas nitriding, so that the hole sealing effect is better, but the AlN has high brittleness, the coating is easy to damage, and the surface smoothness of the coating is poor.
The invention patent with publication number CN108179385B discloses a method for preparing a thread wear-resistant corrosion-resistant anti-lock coating by multi-arc ion plating, which comprises the steps of polishing, ultrasonic cleaning and drying metal threads in sequence, then carrying out sand blasting coarsening on the dried metal threads, then carrying out sputtering cleaning to obtain surface-activated metal threads, and carrying out film coating, wherein the film coating is carried out twice, Ni is firstly plated to be used as a transition layer, and then secondary film coating is carried out on the metal threads with the Ni transition layer on the surface by adopting a cathode arc source made of Ag and Pd to prepare the metal threads with the Ni-AgPd coating on the surface. In the process of preparing the Ni-AgPd coating on the surface of the thread by adopting multi-arc ion plating, the wear resistance of the Ni-AgPd coating is ensured by adding Pd, the thermal stability and the corrosion resistance of the Ni-AgPd coating are improved, and the problem of locking of a fastener is solved. However, once the coating is porous or scratched, the corrosion of the metal thread is accelerated, the risk of thread lock is increased, and the surface smoothness of the obtained coating is poor.
The invention patent with publication number CN106591784B discloses a method for preparing a TiAlSiCN coating by ion plating, which adopts multi-arc ion plating as a preparation technology, and the method comprises the steps of grinding a substrate, cleaning the substrate by using an organic solvent, drying the substrate, then carrying out ion cleaning, then preparing a TiN transition layer, then preparing the TiAlSiCN coating, and polishing the prepared TiAlSiCN coating. The TiAlSiCN coating prepared by the method can solve the problem of short service life of the cutter caused by low hardness of the cutter in the machining process to a certain extent. But the coating is poorly bonded to the substrate.
Disclosure of Invention
In view of the problems of poor bonding strength between the coating and the base material, insufficient surface smoothness of the coating and the like in the prior art, the invention aims to solve the technical problem of obtaining the coating which has high bonding strength with the base material, is smooth and compact, is wear-resistant and corrosion-resistant, and is safe and antibacterial.
In order to realize the aim, the invention provides a multi-arc ion plating coating process, which comprises the following process steps:
step 1, base material pretreatment: immersing the base material in water, absolute ethyl alcohol and acetone in sequence for ultrasonic treatment for 20-40 minutes, then drying at 45-80 ℃, and performing glow cleaning and metal ion bombardment in sequence to obtain a pretreated base material for later use;
step 2, magnetically controlling the multi-arc ion plating TiN transition coating: in-situ performing after the step 1, opening a nitrogen flow valve, controlling the nitrogen flow to be 180-220 mL/min, electrifying a rotary transverse magnetic field, adjusting the magnetic field frequency and the exciting current, electrifying a Ti target, adjusting the bias voltage to be 100-130V, and adjusting the arc target current to be 45-55A, and performing film coating for 6-10 minutes to obtain a TiN transition coating;
step 3, magnetically controlling the multi-arc ion plating of the TiTaN coating: performing in-situ operation after the step 2, controlling the flow of argon gas to be 50-100 mL/min, opening a nitrogen flow valve, controlling the flow of nitrogen gas to be 100-250 mL/min, electrifying a TaTi target, adjusting the bias voltage to be 100-150V, and adjusting the current of an arc target to be 50-80A, and performing film coating for 30-60 minutes to obtain TiTaN;
step 4, magnetically controlling multi-arc ion plating of the TiTaN-BiScCoCN composite multi-element coating: after the step 3, in-situ operation is carried out, argon is continuously introduced at the flow rate of 50-100 mL/min, a nitrogen flow valve is opened, the flow rate of nitrogen is controlled to be 100-250 mL/min, the BiScC target is electrified, the bias voltage is adjusted to be 150-300V, and the arc target current is 50-80A; electrifying the Co target, adjusting the bias voltage to be 140-300V, and adjusting the arc target current to be 50-60A; and keeping the state for coating for 45-90 minutes to obtain the TiTaN-BiScCoCN composite multi-element coating.
Preferably, the base material in step 1 is one of a ferrous material, a stainless steel material and a ceramic material.
Preferably, the glow cleaning is to place the dried substrate in a multi-arc ion plating vacuum chamber, and vacuumize the substrate until the vacuum pressure is 1 × 10 -3 ～5×10 -3 Pa, introducing argon gas with the flow rate of 100-180 mL/min, controlling the working pressure to be 0.05-0.1 Pa, adjusting the bias voltage to be 500-1000V, and cleaning for 15-25 min.
Preferably, the target is a circular target with a large plane and a small thickness, the size is 50-300 mm in diameter, and the thickness is 1-10 mm.
Preferably, the metal ion bombardment is performed in situ after glow cleaning, the Ti target, the TaTi target, the BiScC target and the Co target are started, the transverse magnetic field is rotated and electrified, the magnetic field frequency and the exciting current are adjusted, and the bombardment time is 5-12 min.
Preferably, a rotary transverse magnetic field device is arranged on a flange on the side surface of the target outside the multi-arc ion plating vacuum chamber, and a magnetic conduction ring is arranged around the target.
More preferably, the rotating transverse magnetic field device is composed of a 24-level magnetic circuit framework which can adjust frequency and voltage, has 120-degree phase difference and is controlled by three-phase SPWM waveform (approximate sine wave) current, and winding inserting wires adopt the distribution rule of 24-slot 4/2 polar Δ/2Y (Y is 10) double-speed windings.
More preferably, the frequency of the rotating transverse magnetic field is 100 to 210Hz, and the exciting current is 8 to 12A.
Further, the preparation method of the BiScC target comprises the following steps of:
s1, adding 85-95 parts of high-purity bismuth and 5-15 parts of pure scandium into a crucible, vacuumizing to 0.15-0.25 Pa, smelting at 1540-1550 ℃ until the metal is completely melted, keeping the vacuum state, cooling to 700-900 ℃, uniformly stirring, pouring, cooling to 20-35 ℃ in the vacuum state, forming, taking out and sealing to obtain a Bi-Sc alloy;
s2, putting 30-60 parts of the Bi-Sc alloy prepared in the step S1 and 2-10 parts of graphene into a crucible, vacuumizing to 0.15-0.25 Pa, smelting at 1540-1550 ℃ until the alloy is completely molten, keeping the vacuum state, cooling to 400-600 ℃, uniformly stirring, adding 30-50 parts of high-purity bismuth until the bismuth is completely molten, pouring, cooling to 20-35 ℃ in the vacuum state, and forming to obtain the BiScC target.
Preferably, the material of the casting mold in the step S1 is 310S stainless steel, the diameter is 5-10 cm, and the height is 5-20 cm; and S2, the casting mold is made of 310S stainless steel, the diameter is 80-120 mm, and the thickness is 2-5 mm.
The invention pretreats the base material, cleans the base material and the target material by using glow cleaning and ion bombardment methods, and then carries out multi-arc ion plating on the base material under the magnetic field arc control technology to obtain the TiTaN-BiScCoCN composite multi-element coating. The base material is subjected to glow cleaning and ion bombardment cleaning in sequence before multi-arc ion plating, and the magnetic field is adjusted in the bombardment process, so that the surface of the base material is etched more uniformly, and the binding force between a subsequent coating and the base material is improved. The multi-arc ion plating is carried out by controlling the uniform dispersion of the arc spots through controlling the magnetic field, and the particles are refined, so that the plating layer is smoother and more compact. The coating sequence is as follows: firstly plating a TiN transition film, then plating a TiTaN coating, and finally plating a TiTaN-BiScCoCN composite multi-element coating, so that the components of the coating are in a transition form from the substrate to the TiTaN-BiScCoCN composite multi-element coating, elements at the interface of the coating are mutually diffused, and the compactness of the coating is improved. The TaTi target TiTaN coating is started before the TiTaN-BiScCoCN composite multi-element coating is plated, the Ta diffusion coefficient is small, and the Ta diffusion coefficient is combined with Ti and N, so that an isolation layer is formed on the surface of a base material, mutual diffusion between Bi and Sc and the base material is reduced, the mechanical property of the base material is prevented from being reduced, and the bonding strength between the coating and the base material and the high-temperature oxidation resistance of the coating are further improved; in the process of plating the TiTaN-BiScCoCN composite multi-element coating, the electromigration of Co is less, the perfection degree of the coating gap is improved, the coating is more compact, and meanwhile, the heat conductivity coefficient of the coating is improved by adding Co; ta and Co interact with each other, and the compactness and high-temperature oxidation resistance of the coating are further improved. In addition, in the ion plating process, Bi and Co are doped, so that the electronic migration of Bi in the coating is inhibited, the coating is more compact, and the condition that the coating deforms at high and low temperatures is relieved. The TiTaN-BiScCoCN composite multi-element coating obtained after nitridation has stronger salt corrosion resistance and wear resistance due to the interaction of all elements in ion plating.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages: 1) the method carries out glow cleaning on the base material before multi-arc ion plating and ion bombardment on the base material under the action of a magnetic field, so that the etching on the surface of the base material is more uniformly dispersed, and the bonding strength of a plated coating and the surface of the base material is improved; 2) the invention adopts the large-plane small-thickness circular target material, uses the magnetic field arc control technology in the multi-arc ion plating process, disperses arc spots, refines particles, and ensures that the obtained coating is smoother and more compact and has better bonding property with the base material; 3) in the process of multi-arc ion plating, firstly, the TaTi target plated TiTaN coating is started between the TiN transition layer and the TiTaN-BiScCoCN plated composite multi-element coating, so that the bonding strength between the coating and the base material is improved, the compactness of the coating is improved, nitridation and multi-arc ion plating of a BiScC target and a Co target are carried out, the compactness and the high-temperature oxidation resistance of the TiTaN-BiScCoCN composite multi-element coating are further improved, the deformation condition of the coating in high-temperature and low-temperature transition is relieved, and meanwhile, the TiTaN-BiScCoCN composite multi-element coating also has good wear resistance and salt corrosion resistance.
Glow cleaning: glow cleaning, also known as glow discharge cleaning, is a more specialized vacuum system and material cleaning method, and is commonly used for cleaning and degassing in high vacuum and ultra-high vacuum systems. Gas desorption by electron bombardment and removal of certain hydrocarbons can be achieved by using a hot filament or electrode as an electron source, on which a negative bias is applied with respect to the surface to be cleaned. Inert gases (such as argon, helium and the like) with proper partial pressure need to be filled in the cleaning process, and the typical working pressure of the discharge gas is between 0.05 and 10 Pa. The inert gas is ionized in the discharging process and bombards the inner wall of the vacuum chamber and other components in the vacuum chamber to realize cleaning. And because of the characteristics of the inert gas, the inert gas is easier to be pumped away by a vacuum system after replacing other gases adsorbed on the surface layer of the wall, and is beneficial to obtaining and maintaining ultrahigh vacuum.
The metal ion bombardment can remove the pollution layer and oxide on the surface of the base material and also can increase the surface roughness of the base material.
Detailed Description
The raw materials of the examples and the comparative examples are as follows:
stainless steel substrate: jiangsu Hongze metal materials Co Ltd, the material is: 304 with a thickness of 1.5 mm.
Ti target: beijing li Chuanxin metal material science and technology Limited, specification: diameter 254mm, thickness 10mm, purity: the mass fraction of Ti contained is more than or equal to 99.865 percent.
TaTi target: changxain kang new materials, ltd, purity: 99.9, specification: the diameter is 50.8mm, and the thickness is 3 mm.
Co target: changxain new materials, ltd., purity: co: 99.98 wt%, specification: the diameter is 50.8mm, and the thickness is 3.175 mm.
Graphene: shenzhen Tuoling evolution technology Limited, specific surface area: 50-200 m 2 Per g, particle size D 90 : 11 to 15 μm, particle size D 50 : 7-12 μm, thickness: 1-3 layers.
Example 1
A multi-arc ion plating coating process comprises the following process steps:
step 1, pretreatment: sequentially immersing a stainless steel substrate with the size of 10mm multiplied by 5mm multiplied by 1.5mm in water, absolute ethyl alcohol and acetone for 30 minutes by ultrasonic treatment, then drying at 60 ℃, putting the dried substrate into a multi-arc ion plating vacuum chamber, and vacuumizing until the vacuum pressure is 3 multiplied by 10 -3 Pa, introducing argon gas with the flow rate of 150mL/min, controlling the working pressure to be 0.08Pa, opening the bias voltage to be 800V, cleaning for 20 minutes, then opening the Ti target, the TaTi target, the BiScC target and the Co target, electrifying by rotating a transverse magnetic field, adjusting the frequency of the magnetic field to be 150Hz, exciting current to be 11A, and bombarding for 8 minutes by ions to obtain a pretreated base material for later use;
step 2, magnetically controlling the multi-arc ion plating TiN transition coating: performing in-situ after the step 1, opening a nitrogen flow valve, controlling the nitrogen flow to be 200mL/min, electrifying a rotary transverse magnetic field, adjusting the magnetic field frequency to be 150Hz, exciting current to be 11A, electrifying a Ti target, adjusting the bias voltage to be 110V and the arc target current to be 50A, and performing film coating for 8 minutes to obtain a TiN transition coating;
step 3, magnetically controlling the multi-arc ion plating of the TiTaN coating: performing in-situ operation after the step 2, controlling the flow of argon gas to be 80mL/min, opening a nitrogen flow valve, controlling the flow of nitrogen gas to be 160mL/min, electrifying a TaTi target, adjusting the bias voltage to be 130V and the arc target current to be 60A, and performing film coating for 45 minutes to obtain a TiTaN coating;
step 4, magnetically controlling the multi-arc ion plating of the TiTaN-BiScCoCN composite multi-element coating: after the step 3, in-situ operation is carried out, argon is continuously introduced at 80mL/min, a nitrogen flow valve is opened, the nitrogen flow is controlled to be 160mL/min, the BiScC target is electrified, the bias voltage is adjusted to be 220V, and the arc target current is 70A; electrifying the Co target, adjusting the bias voltage to 225V and the arc target current to 55A; and keeping the state for coating for 60 minutes to obtain the TiTaN-BiScCoCN composite multi-element coating.
The preparation method of the BiScC target comprises the following steps:
s1, adding 2000g of high-purity bismuth and 222g of pure scandium into a crucible, vacuumizing to 0.2Pa, smelting at 1500 ℃ until the metal is completely molten, keeping the vacuum state, cooling to 800 ℃, uniformly stirring, pouring by using a die with the diameter of 8cm and the height of 15cm, cooling to 25 ℃ in the vacuum state, forming, taking out and sealing to obtain a Bi-Sc alloy;
s2, putting 889g of the Bi-Sc alloy prepared in the step S1 and 111g of graphene into a crucible, vacuumizing to 0.2Pa, smelting at 1545 ℃ until the alloy is completely molten, keeping the vacuum state, cooling to 500 ℃, uniformly stirring, adding 1111g of high-purity bismuth until the bismuth is completely molten, pouring by using a die with the diameter of 100mm and the height of 3mm, and cooling to 25 ℃ in the vacuum state for molding to obtain the BiScC target.
Comparative example 1
A multi-arc ion plating coating process comprises the following process steps:
step 1, pretreatment: immersing stainless steel substrate with size of 10mm × 5mm × 1.5mm in water, anhydrous ethanol, and acetone sequentially, ultrasonically treating for 30 min, drying at 60 deg.C, placing the dried substrate in a multi-arc ion plating vacuum chamber, and vacuumizing to vacuum pressure of 3 × 10 -3 Pa, introducing argon gas with the flow rate of 150mL/min, controlling the working pressure to be 0.08Pa, opening the bias voltage to be 800V, cleaning for 20 minutes, then opening the Ti target, the BiScC target and the Co target, electrifying by rotating a transverse magnetic field, adjusting the frequency of the magnetic field to be 150Hz, exciting current to be 11A, and bombarding ions for 8 minutes to obtain a pretreated base material for later use;
step 2, magnetically controlling the multi-arc ion plating TiN transition coating: in-situ processing is carried out after the step 1, a nitrogen flow valve is opened, the nitrogen flow is controlled to be 200mL/min, a transverse magnetic field is rotated and electrified, the magnetic field frequency is adjusted to be 150Hz, the exciting current is 11A, a Ti target is electrified, the bias voltage is adjusted to be 110V, the arc target current is 50A, film coating is carried out, the film coating time is 8 minutes, and the TiN transition coating is obtained;
step 3, magnetically controlled multi-arc ion plating of the TiN-BiScCoCN composite multi-element coating: after the step 2, in-situ operation is carried out, argon is continuously introduced at 80mL/min, a nitrogen flow valve is opened, the nitrogen flow is controlled to be 160mL/min, the BiScC target is electrified, the bias voltage is adjusted to be 220V, and the arc target current is 70A; electrifying the Co target, adjusting the bias voltage to 225V and the arc target current to 55A; and keeping the state for film coating for 60 minutes to obtain the TiN-BiScCoCN composite multi-element coating.
The method for preparing the BiScC target is the same as that of example 1.
Comparative example 2
A multi-arc ion plating coating process comprises the following process steps:
step 1, pretreatment: immersing stainless steel substrate with size of 10mm × 5mm × 1.5mm in water, anhydrous ethanol, and acetone sequentially, ultrasonically treating for 30 min, drying at 60 deg.C, placing the dried substrate in a multi-arc ion plating vacuum chamber, and vacuumizing to vacuum pressure of 3 × 10 -3 Pa, introducing argon gas with the flow rate of 150mL/min, controlling the working pressure to be 0.08Pa, opening the bias voltage to be 800V, cleaning for 20 minutes, then opening the Ti target, the TaTi target and the BiScC target, electrifying by rotating a transverse magnetic field, adjusting the frequency of the magnetic field to be 150Hz, exciting current to be 11A, and bombarding the ions for 8 minutes to obtain a pretreated base material for later use;
step 2, magnetically controlling the multi-arc ion plating TiN transition coating: in-situ processing is carried out after the step 1, a nitrogen flow valve is opened, the nitrogen flow is controlled to be 200mL/min, a transverse magnetic field is rotated and electrified, the magnetic field frequency is adjusted to be 150Hz, the exciting current is 11A, a Ti target is electrified, the bias voltage is adjusted to be 110V, the arc target current is 50A, film coating is carried out, the film coating time is 8 minutes, and the TiN transition coating is obtained;
step 3, magnetically controlling the multi-arc ion plating of the TiTaN coating: performing in-situ after the step 2, controlling the flow of argon gas to be 80mL/min, opening a nitrogen flow valve, controlling the flow of nitrogen gas to be 160mL/min, electrifying a TaTi target, adjusting the bias voltage to be 130V, and adjusting the current of an arc target to be 60A, and performing film coating for 45 minutes to obtain a TiTaN coating;
step 4, magnetically controlling the multi-arc ion plating of the TiTaN-BiScCN composite multi-element coating: and (3) continuing to introduce argon at the rate of 80mL/min, opening a nitrogen flow valve, controlling the nitrogen flow at 160mL/min, electrifying the BiScC target, adjusting the bias voltage to 220V and the arc target current to 70A, keeping the state, and performing film coating for 60 minutes to obtain the TiTaN-BiScCN composite multi-element coating.
The method for preparing the BiScC target is the same as that of example 1.
Comparative example 3
A multi-arc ion plating coating process comprises the following process steps:
step 1, pretreatment: immersing stainless steel substrate with size of 10mm × 5mm × 1.5mm in water, anhydrous ethanol, and acetone sequentially, ultrasonically treating for 30 min, drying at 60 deg.C, placing the dried substrate in a multi-arc ion plating vacuum chamber, and vacuumizing to vacuum pressure of 3 × 10 -3 Pa, introducing argon gas with the flow rate of 150mL/min, controlling the working pressure to be 0.08Pa, opening the bias voltage to be 800V, cleaning for 20 minutes, then opening the Ti target, the TaTi target and the Co target, electrifying by rotating a transverse magnetic field, adjusting the frequency of the magnetic field to be 150Hz, exciting current to be 11A, and bombarding ions for 8 minutes to obtain a pretreated base material for later use;
step 2, magnetically controlling the multi-arc ion plating TiN transition coating: in-situ processing is carried out after the step 1, a nitrogen flow valve is opened, the nitrogen flow is controlled to be 200mL/min, a transverse magnetic field is rotated and electrified, the magnetic field frequency is adjusted to be 150Hz, the exciting current is 11A, a Ti target is electrified, the bias voltage is adjusted to be 110V, the arc target current is 50A, film coating is carried out, the film coating time is 8 minutes, and the TiN transition coating is obtained;
step 3, magnetically controlling the multi-arc ion plating of the TiTaN coating: performing in-situ operation after the step 2, controlling the flow of argon gas to be 80mL/min, opening a nitrogen flow valve, controlling the flow of nitrogen gas to be 160mL/min, electrifying a TaTi target, adjusting the bias voltage to be 130V and the arc target current to be 60A, and performing film coating for 45 minutes to obtain a TiTaN coating;
step 4, magnetically controlling the multi-arc ion plating of the TiTaN-CoN composite multi-element coating: and (3) continuing to introduce argon gas at a rate of 80mL/min, opening a nitrogen flow valve, controlling the nitrogen flow at 160mL/min, electrifying the Co target, adjusting the bias voltage to 225V and the arc target current to 55A, keeping the state, and performing coating for 60 minutes to obtain the TiTaN-CoN composite multi-element coating.
Comparative example 4
A multi-arc ion plating coating process comprises the following process steps:
step 1, pretreatment: immersing stainless steel substrate with size of 10mm × 5mm × 1.5mm in water, anhydrous ethanol, and acetone sequentially, ultrasonically treating for 30 min, drying at 60 deg.C, placing the dried substrate in a multi-arc ion plating vacuum chamber, and vacuumizing to vacuum pressure of 3 × 10 -3 Pa, introducing argon gas with the flow rate of 150mL/min, controlling the working pressure to be 0.08Pa, opening the bias voltage to be 800V, cleaning for 20 minutes, then opening the Ti target, the TaTi target, the BiScC target and the Co target, electrifying by rotating a transverse magnetic field, adjusting the frequency of the magnetic field to be 150Hz, exciting current to be 11A, and bombarding for 8 minutes by ions to obtain a pretreated base material for later use;
step 2, magnetically controlling the multi-arc ion plating TiN transition coating: performing in-situ after the step 1, opening a nitrogen flow valve, controlling the nitrogen flow to be 200mL/min, electrifying a rotary transverse magnetic field, adjusting the magnetic field frequency to be 150Hz, exciting current to be 11A, electrifying a Ti target, adjusting the bias voltage to be 110V and the arc target current to be 50A, and performing film coating for 8 minutes to obtain a TiN transition coating;
step 3, magnetic control multi-arc ion plating of a TiCoN coating: performing in-situ operation after the step 2, controlling the flow of argon gas to be 80mL/min, opening a nitrogen flow valve, controlling the flow of nitrogen gas to be 160mL/min, electrifying a Co target, adjusting the bias voltage to be 225V, and the current of an arc target to be 55A, and performing film coating for 45 minutes to obtain a TiTaN coating;
step 4, magnetically controlling multi-arc ion plating of a TiCoN-BiScTaCN composite multi-element coating: after the step 3, the in-situ operation is carried out, argon gas is continuously introduced at the flow rate of 80mL/min, a nitrogen flow valve is opened, the flow rate of the nitrogen gas is controlled to be 160mL/min, the BiScC target is electrified, the bias voltage is adjusted to be 220V, and the arc target current is adjusted to be 70A; electrifying the TiTa target, adjusting the bias voltage to 130V and the arc target current to 60A; and keeping the state for film coating for 60 minutes to obtain the TiCoN-BiScTaCN composite multi-element coating.
The method for preparing the BiScC target is the same as that of example 1.
Test example 1
And (3) testing the binding force of the coating and the substrate:
according to a doctor paper (the performance research of the tantalum-based nanocrystalline coating in a simulated biological environment, the author: Liulin, Nanjing aerospace university, 2017) by adopting a scratch experiment to determine the binding force method, a Nano Indenter with the model number of Nano indicator G200 is used for testing the binding force of a coating sample and a substrate, and the test conditions are as follows: the maximum load is set to be 80mN, the scratch speed is 10 μm/s, the scratch length is 500 μm, the vertical load applied to the indenter in the scratch process is increased from 30 μ N to the set maximum load of 80mN, the change of an acoustic emission signal of the instrument is monitored, when the acoustic emission signal is suddenly increased, the coating is shown to be peeled off, the load is critical load Lc at the moment, the bonding strength between the coating and the base material is shown, and the result is shown in Table 1.
Test example 2
And (3) testing the wear resistance of the coating:
referring to journal papers (performance research of multi-arc ion plating ZrN plating on stainless steel surface, author: dawn et al, metallic materials and metallurgy engineering, 2021), friction performance test was performed on MS-T3000 friction wear tester, the coated sample was fixed on a test platform, a rolling friction type abrasion test was performed for 30 minutes with a 45 steel ring, and the weight of the sample before and after abrasion was measured, and the abrasion condition was measured as the sample mass loss before and after abrasion, and the results are shown in Table 1.
Test example 3
Testing the corrosion resistance of the coating to hot salt:
the hot salt corrosion test is carried out on a coating sample by referring to a master paper (preparation of a multi-arc ion plating NiSiAlY coating and hot salt corrosion performance research, author: Tore Cheng, Nibo materials technology and engineering research institute of Chinese academy of sciences, 2020), and the test steps are as follows: 1) brushing salt on the surface of the coating sample and drying at 45 ℃ to obtain the coating with the salt content of 5mg/cm on the surface 2 (ii) a 2) Heating the muffle furnace to 600 ℃, putting the coating sample obtained in the step 1) into a clean crucible, then putting the crucible into the muffle furnace at 600 ℃, standing for 4 hours, and observing the corrosion condition of the surface of the coating, wherein the results are shown in table 1 in terms of obvious corrosion, slight corrosion and no corrosion.
TABLE 1 coating Performance test results
(remarks: the more severe the scratch, the poorer the bond between the coating and the substrate, the more slight the scratch, the better the bond between the coating and the substrate, the smaller the amount of wear, the better the abrasion resistance, the larger the amount of wear, the worse the abrasion resistance.)
The comparison between the example 1 and the comparative examples 1 to 3 shows that the bonding force, the wear resistance and the salt corrosion resistance of the coating and the base material in the example 1 are all superior to those in the comparison of 1 to 3, probably because the base material is etched before being coated in the example 1, the surface roughness of the base material is increased and uniformly dispersed, and the coating and the base material are better bonded during ion coating; when in film plating, the TaTi target is firstly started, then the BiScC target and the Co target are started, nitrogen is introduced, and the elements such as Ta, Co, Bi and the like interact with each other, so that the coating is more compact and wear-resistant, the bonding strength of the coating and the base material is further improved, and meanwhile, the heat-resistant salt corrosion resistance of the coating is also improved.
Claims (10)
1. The multi-arc ion plating coating process is characterized by comprising the following steps of:
step 1, base material pretreatment;
step 2, magnetically controlling the multi-arc ion plating of a TiN transition coating;
step 3, carrying out magnetic control multi-arc ion plating on the TiTaN coating;
and 4, magnetically controlling the multi-arc ion plating of the TiTaN-BiScCoCN composite multi-element coating.
2. The multi-arc ion plating coating process of claim 1, comprising the steps of:
step 1, base material pretreatment: immersing the base material in water, absolute ethyl alcohol and acetone in sequence for ultrasonic treatment for 20-40 minutes, then drying at 45-80 ℃, and performing glow cleaning and metal ion bombardment in sequence to obtain a pretreated base material for later use;
step 2, magnetic control multi-arc ion plating of TiN transition coating: performing in-situ after the step 1, opening a nitrogen flow valve, controlling the nitrogen flow to be 180-220 mL/min, electrifying a rotary transverse magnetic field, adjusting the magnetic field frequency and the exciting current, electrifying a Ti target, adjusting the bias voltage to be 100-130V, adjusting the arc target current to be 45-55A, and performing film coating for 6-10 minutes to obtain a TiN transition coating;
step 3, magnetically controlling the multi-arc ion plating of the TiTaN coating: performing in-situ operation after the step 2, controlling the flow of argon gas to be 50-100 mL/min, opening a nitrogen flow valve, controlling the flow of nitrogen gas to be 100-250 mL/min, electrifying a TaTi target, adjusting the bias voltage to be 100-150V, and adjusting the current of an arc target to be 50-80A, and performing film coating for 30-60 minutes to obtain TiTaN;
step 4, magnetically controlling the multi-arc ion plating of the TiTaN-BiScCoCN composite multi-element coating: after the step 3, introducing argon continuously at a rate of 50-100 mL/min, opening a nitrogen flow valve, controlling the nitrogen flow at 100-250 mL/min, electrifying the BiScC target, adjusting the bias voltage at 150-300V, and adjusting the arc target current at 50-80A; electrifying the Co target, adjusting the bias voltage to be 140-300V, and adjusting the arc target current to be 50-60A; and keeping the state for coating for 45-90 minutes to obtain the TiTaN-BiScCoCN composite multi-element coating.
3. The multi-arc ion plating coating process of claim 1 or 2, wherein: the base material is one of an iron material, a stainless steel material and a ceramic material.
4. The multi-arc ion plating coating process of claim 1 or 2, wherein the BiScC target is prepared by the following steps in parts by weight:
s1, adding 85-95 parts of high-purity bismuth and 5-15 parts of pure scandium into a crucible, vacuumizing to 0.15-0.25 Pa, smelting at 1540-1550 ℃ until the metal is completely melted, keeping the vacuum state, cooling to 700-900 ℃, uniformly stirring, pouring, cooling to 20-35 ℃ in the vacuum state, forming, taking out and sealing to obtain a Bi-Sc alloy;
s2, putting 30-60 parts of the Bi-Sc alloy prepared in the step S1 and 2-10 parts of graphene into a crucible, vacuumizing to 0.15-0.25 Pa, smelting at 1540-1550 ℃ until the alloy is completely molten, keeping the vacuum state, cooling to 400-600 ℃, uniformly stirring, adding 30-50 parts of high-purity bismuth until the bismuth is completely molten, pouring, cooling to 20-35 ℃ in the vacuum state, and forming to obtain the BiScC target.
5. The multi-arc ion plating coating process of claim 4, wherein: s1, the casting mold is made of 310S stainless steel, the diameter is 5-10 cm, and the height is 5-20 cm; and S2, the casting mold is made of 310S stainless steel, the diameter of the casting mold is 80-120 mm, and the thickness of the casting mold is 2-5 mm.
6. The multi-arc ion plating coating process of claim 2, wherein: the glow cleaning is to put the dried base material into a multi-arc ion plating vacuum chamber and vacuumize the base material until the vacuum pressure is 1 multiplied by 10 -3 ～5×10 -3 Pa, introducing argon with the flow rate of 100-180 mL/min, controlling the working pressure to be 0.05-0.1 Pa, and opening the bias voltage to be-1000 to-500V, and cleaning for 15-25 min.
7. The multi-arc ion plating coating process of claim 2, wherein: the target is a circular target with a large plane and a small thickness, the size is 50-300 mm in diameter, and the thickness is 1-10 mm.
8. The multi-arc ion plating coating process of claim 2, wherein: and the metal ion bombardment is performed in situ after glow cleaning, the Ti target, the TaTi target, the BiScC target and the Co target are started, the transverse magnetic field is rotated and electrified, the magnetic field frequency and the exciting current are adjusted, and the bombardment time is 5-12 min.
9. The multi-arc ion plating coating process of claim 2, wherein: the frequency of the rotating transverse magnetic field is 100-210 Hz, and the exciting current is 8-12A.
10. A TiTaN-BiScCoCN composite multi-element coating is characterized in that: the coating is prepared by the multi-arc ion plating coating process of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210539640.4A CN114921759B (en) | 2022-05-17 | 2022-05-17 | Multi-arc ion plating coating process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210539640.4A CN114921759B (en) | 2022-05-17 | 2022-05-17 | Multi-arc ion plating coating process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114921759A true CN114921759A (en) | 2022-08-19 |
| CN114921759B CN114921759B (en) | 2023-08-04 |
Family
ID=82807978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210539640.4A Active CN114921759B (en) | 2022-05-17 | 2022-05-17 | Multi-arc ion plating coating process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114921759B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0410337A2 (en) * | 1989-07-28 | 1991-01-30 | BASF Aktiengesellschaft | Protection coatings made of germanium ceramics |
| US5892424A (en) * | 1995-02-10 | 1999-04-06 | The Furukawa Electric Co., Ltd. | Encapsulated contact material and a manufacturing method therefor, and a manufacturing method and a using method for an encapsulated contact |
| US20080280050A1 (en) * | 2006-01-11 | 2008-11-13 | Evonik Degussa Gmbh | Ceramic Wall Cladding Composites with Electromagnetic Shielding Properties |
| RU89105U1 (en) * | 2009-06-01 | 2009-11-27 | Федеральное государственное образовательное учреждение высшего профессионального образования "Ульяновская государственная сельскохозяйственная академия" | MULTI-LAYER CUTTING TOOL |
| US20100159239A1 (en) * | 2006-02-20 | 2010-06-24 | Evonik Degussa Gmbh | Method for coating substrates and carrier substrates |
-
2022
- 2022-05-17 CN CN202210539640.4A patent/CN114921759B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0410337A2 (en) * | 1989-07-28 | 1991-01-30 | BASF Aktiengesellschaft | Protection coatings made of germanium ceramics |
| US5892424A (en) * | 1995-02-10 | 1999-04-06 | The Furukawa Electric Co., Ltd. | Encapsulated contact material and a manufacturing method therefor, and a manufacturing method and a using method for an encapsulated contact |
| US20080280050A1 (en) * | 2006-01-11 | 2008-11-13 | Evonik Degussa Gmbh | Ceramic Wall Cladding Composites with Electromagnetic Shielding Properties |
| US20100159239A1 (en) * | 2006-02-20 | 2010-06-24 | Evonik Degussa Gmbh | Method for coating substrates and carrier substrates |
| RU89105U1 (en) * | 2009-06-01 | 2009-11-27 | Федеральное государственное образовательное учреждение высшего профессионального образования "Ульяновская государственная сельскохозяйственная академия" | MULTI-LAYER CUTTING TOOL |
Non-Patent Citations (1)
| Title |
|---|
| 韩敏芳: "固体氧化物燃料电池中的陶瓷材料", 硅酸盐学报 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114921759B (en) | 2023-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Deng et al. | Physical vapor deposition technology for coated cutting tools: A review | |
| CN109943824B (en) | Preparation method of high-hardness conductive carbon-based film | |
| CN109778136B (en) | Method for preparing diamond-like coating by adopting thermionic plasma technology | |
| CN108707868B (en) | Vacuum ion plating Ag nano composite coating fastener and preparation method thereof | |
| CN108374154B (en) | Diamond-like carbon coating preparation device with composite magnetic field and application thereof | |
| JP4300762B2 (en) | Carbon film-coated article and method for producing the same | |
| CN111321381B (en) | AlCrNbSiTiBN-based nano composite coating of hard alloy blade and preparation method thereof | |
| CN108977759B (en) | Method for carrying out composite strengthening treatment on metal plasma immersion ion implantation and deposition on surface of spallation target ball | |
| CN112501569B (en) | Surface gradient high-entropy alloy layer and preparation method thereof | |
| CN114351110B (en) | Reinforced diamond-like film and preparation method thereof | |
| CN112981320A (en) | Titanium alloy surface composite coating and preparation method thereof | |
| CN108468030B (en) | Magnetron sputtering method for silver plating on surface of copper contact | |
| CN110724923A (en) | Preparation method of ion-impregnated tungsten carbide layer with surface gradient nanostructure | |
| CN110373632B (en) | Die-casting aluminum die with nanocrystalline composite coating and preparation method | |
| CN102534514A (en) | Method for plating films of multi-arc ion plating | |
| CN114632909A (en) | Method for preparing carbon oxygen nitrogen coating by ion implantation on surface of die-casting die | |
| CN104975263A (en) | Multi-stage magnetic field arc ion plating and radio-frequency magnetron sputtering composite deposition method | |
| CN104894515A (en) | Electric-arc ion plating method for forming CuCr coating on surface of CuCr contact | |
| CN108611590B (en) | Method for preventing Ti alloy workpiece from being seized | |
| CN210506503U (en) | Die-casting aluminum die with nanocrystalline composite coating | |
| RU2379378C2 (en) | Method of ion-plasma spraying coating of multicomponent film coatings and installation for its implementation | |
| CN108165944A (en) | A kind of super thick Ti2The preparation method of AlC coatings | |
| CN114921759B (en) | Multi-arc ion plating coating process | |
| CN115627445B (en) | Anti-adhesion high-entropy boride composite coating for aluminum die-casting die and preparation method of composite coating | |
| CN108796493B (en) | Hole sealing modification method for cold spraying coating on surface of light metal |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: No. 81, Ehu Road, Ehu Town, Xishan District, Wuxi City, Jiangsu Province, 214000 Applicant after: Wuxi Qiantai New Material Technology Co.,Ltd. Address before: Xiyang Line, Dongfeng Community, Qianqiao Street, Huishan District, Wuxi City, Jiangsu Province, 214000 Applicant before: Wuxi Qiantai New Material Technology Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |