CN101698363A - TiN/(TiN+CrN)/CrAlN nano composite coating and preparation method thereof - Google Patents
TiN/(TiN+CrN)/CrAlN nano composite coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a TiN/(TiN+CrN)/CrAlN nano composite coating and a preparation method thereof. The nano composite multilayer coating is a multilayer metal nitride ceramic coating which has a TiN/(TiN+CrN)/CrAlN structure and is formed sequentially by a transitional layer TIN membrane, a (TiN+CrN) nano composite multilayer and a CrAlN nano composite multilayer on a tool or mold matrix made of hard alloy, high-speed steel and heat-resistance mold steel. The preparation method comprises preheating, surface cleaning and etching, the preparation of the transitional layer, the preparation of the (TiN+CrN) nano composite multilayer, the preparation of the CrAlN nano composite multilayer and other steps. In the invention, with a proper coating structural design, the bonding force of CrAlN coatings with the matrix is improved and the high hardness and high-temperature performance of the CrAlN coatings are retained.
Description
Technical field
The present invention relates to worker, mould nano-composite coating, be specifically related to a kind of TiN/ (TiN+CrN)/CrAlN nano-composite coating and preparation method thereof.
Background technology
Over nearly 20 years, utilize physical gas phase deposition technology (PVD) to be subjected to extensive concern in the application that worker, die surface prepare advanced hard coat.TiAlN, AlTiN, AlCrN, TiSiN, Al have not only appearred
2O
3Deng wear-resistant coating, also has MoS
2, various lubricant coatings such as DLC, WC/C, and new coating structure such as gradient coating, nano-composite coating greatly improves the performance of coating.Composite multilayer membrane, nano composite multiple layer film become the important directions of present superhard coating technical development.These coatings not only are applied to the cutting tool field, also obtain to a certain degree application at die industry.The hardness of coating, high temperature resistant property and coating become the important indicator of assessment coating quality with high base strength.
CrN is that the oxidizing temperature of coating is approximately 600 ℃.Discovering after the nineties, part Al substitutes hardness and the red hardness that Cr can further improve coating in the coating.Al content is the key factor that influences coating hardness and oxidation resistance in the CrAlN system.Cr
0.40Al
0.60The N film is better than Cr
0.77Al
0.23N film (J.Lin, B.Mishra, Surface﹠amp; CoatingsTechnology 202 (2008): 3272-3283), hardness is brought up to 36Gpa from 25GPa, and Young's modulus of elasticity is brought up to 380GPa from 280GPa; And the former is behind 800 ℃ of annealing 1 lab scales, and the hardness of coating still can remain on more than the 25GPa.CrAlN (the CRONITE of Balzers company release in 2006
TR) serial coating has the excellent comprehensive performance, the usage range of this coating is very wide, being worked into High-speed machining from middle and slow speed of revolution all can be practical, and when middle and slow speed of revolution the working (machining) efficiency and the life-span of this coating obviously be better than a large amount of at present advanced coatings of using of TiAlN series.But this coating technology scheme is still business secret.
After Al substituted Cr, internal stress increased considerably in the coating, the bond strength of the coating-substrate alloy that weakened.The composite coating technology is the effective way that addresses this problem.TiN/CrAlN composite multi-layer structure can reduce coating internal stress (M.Okumiya, Surface and Coatings Technology, 112 (1999): 123-128) greatly.ISCAR company once puts on display tool steel surface PVD Beijing machinery fair in 2005 and coats the TiN coating thick above 1mm, illustrates that the internal stress of TiN coating is extremely low, and coating has excellent toughness.
Chinese invention patent application 200610045989.3 discloses a kind of CrN/CrAlN protective coating that adopts magnetically controlled DC sputtering physical vapor deposition (PVD) method resistance to high temperature corrosion in wide temperature range, the coating internal layer is CrN, and skin is the Cr-Al-N layer of Al content distribution gradient, chemical formula is Cr1-xAlxN, Al content x value excursion 0-0.82 wherein, change in gradient, reaching maximum Cr near coating surface
0.18Al
0.82N.The characteristics of this technology are that coating brought into play tack and the toughness of CrN (internal layer) with the matrix material excellence; The resistance to high temperature corrosion ability that performance Cr1-xAlxN (skin) is excellent; Adopt component gradient to change and reduce residual stress in coating (the composition sudden change is with the thermophysical property parameter, the mechanical property parameters sudden change that bring).But adopt single magnetron sputtering technique,, be difficult to increase substantially the same high base strength of coating because the ionization degree of metallic is low.Thicker in addition, than the CrN internal layer (about 12GPa) of soft will influence whole coating hardness, the infringement abrasion property.
Summary of the invention
The objective of the invention is to overcome the shortcoming that prior art exists, TiN/ (the TiN+CrN)/CrAlN nano-composite coating of a kind of adhesion height that is suitable for using in the tool and mould field, hardness height, high-temperature behavior excellence is provided.
Another object of the present invention is to provide the preparation method of above-mentioned TiN/ (TiN+CrN)/CrAlN nano-composite coating.
Purpose of the present invention is achieved through the following technical solutions:
A kind of TiN/ (TiN+CrN)/CrAlN nano-composite coating: this nanocomposite laminated coating is to be on the instrument or die matrix of carbide alloy, high-speed steel, refractory steel in material, and forming structure by transition zone TiN film, (TiN+CrN) nano composite multiple layer and CrAlN nano composite multiple layer successively is TiN/ (TiN+CrN)/Ti (CN) multiple layer metal nitride ceramics coating.
The preparation method of TiN/ (TiN+CrN)/CrAlN nano-composite coating comprises the steps and process conditions:
(1) instrument or die surface preliminary treatment: place the alkalinous metal cleaning fluid to boil on instrument or mould and carry out surface degreasing; Under the room temperature instrument or mould are placed the ultrasonic processing of ultrasonic cleaning machine that fills the alkalinous metal cleaning fluid; Instrument after will cleaning then or mould are put into the straight alcohol solution dehydrates and are handled the back drying;
(2) preheat: will pack in the reacting furnace through pretreated instrument or mould, and vacuumize and reach 5 * 10
-3Behind the Pa, feed Ar gas, keeping vacuum is 1-4 * 10
-1Pa starts HCD electron gun and body of heater inner heating device; After the starting the arc of HCD electron gun, control HCD electron gun current is 110-180A; The direct-current plasma arc direct irradiation surface of the work in HCD electron gun source reaches 100 ℃-200 ℃ up to the vacuum indoor temperature;
(3) surface clean etching: it is 1-4 * 10 that feeding Ar gas is kept indoor vacuum
-1Pa, adjusting the HCD electron gun current is 120-180A; Workpiece is applied the 300-800V pulsed bias, starter cathode multi sphere titanium target, the titanium ion that sputters out bombards surface of the work under electric field action; Cleaning and lithography tool or die surface under high energy electron and metal ion acting in conjunction; Etching instrument or mould 30-60 minute, the vacuum indoor temperature was no more than 300 ℃;
(4) transition zone preparation: close the negative electrode multi sphere titanium target that step (2) is started, keep Ar gas feeding amount in the step (2), regulate N
2Gas feeding amount makes plated film stove vacuum chamber pressure be increased to 1.1-5.0 * 10
-1Pa; Focus on HCD electron gun direct-current arc in crucible, the HCD electron gun current is 130-180A; Close the HCD electron gun after pure titanium 3-7 minute in the evaporation crucible, close the Ar source of the gas; Regulate N
2Flow, the maintenance vacuum pressure is 0.5-1.5Pa, and workpiece applies the 300-400V bias voltage, starts at least 2 negative electrode multi sphere titanium targets, and target current is 80-90A; Adopt negative electrode multi sphere titanium target to coat 10-20 minute;
(5) (TiN+CrN) nano composite multiple layer preparation: close negative electrode multi sphere titanium target in the step (3); Regulate N
2Flux, the maintenance vacuum indoor pressure is 2.0-10 * 10
-1Pa; Adjust workpiece bias, start 1 negative electrode multi sphere titanium target and 1 negative electrode multi sphere chromium target earlier, workpiece is applied the 200V pulsed bias, close after applying 6-12 minute, target current is 70-80A; Restart 2 negative electrode multi sphere titanium targets and 2 negative electrode multi sphere chromium targets, then workpiece is applied the 150V bias voltage, close after applying 6-12 minute, target current is 70-80A;
(6) CrAlN nano composite multiple layer preparation: only feed N
2, the maintenance vacuum indoor pressure is 1.0-10 * 10
-1Pa; The adjustment workpiece bias is 100-150V, starts at least 2 negative electrode multi sphere CrAl alloys target, and target current is 80-90A, is coated with time 20-40 minute, makes the thickness of whole TiN/ (TiN+CrN)/CrAlN nano-composite coating reach 1-5 μ m; The vacuum chamber temperature was lower than 400 ℃ when coating finished; By weight, the Al composition accounts for 50-70% in the target of described negative electrode multi sphere CrAl alloys target.
For further realizing the object of the invention, the described vacuum of step (1) is preferably 2.3 * 10
-1Pa; The HCD electron gun current is preferably 130-160A.
The described vacuum of step (3) is preferably 2.3 * 10
-1Pa.
The described increase room pressure of step (4) preferably arrives 2.5-4.1 * 10
-1Pa; The HCD electron gun current is preferably 150A; Pure titanium is closed the HCD electron gun after preferred 5 minutes in the evaporation crucible.
Step (5) keeps vacuum indoor pressure to be preferably 0.3-0.5 * 10
-1Pa.
Step (6) keeps vacuum indoor pressure to be preferably 0.3-0.5 * 10
-1Pa; The CrAl alloy target material is Cr
40Al
60Whole coating layer thickness is preferably 2-3.5 μ m.
Compared with prior art, the present invention has the following advantages:
(1) the HCD plasma source is used for heated parts, etching specimen surface, evaporates the energy as Ti in the preparation process.Preparation process requires initial depression＜5 * 10
-3Pa; Temperature is＜400 ℃ in the reacting furnace, can not produce obviously influence to the iron-based matrix material structure.
(2) the transition zone TiN of coating and matrix bond adopts ER and sputter reaction bonded, has avoided the appearance of large-size molten drop particle on the interface, junction, by follow-up high bias sputtering, has further strengthened the same high base strength of this layer.
(3) nano composite multiple layer of TiN/ of the present invention (TiN+CrN)/CrAlN is given full play to the same cermet of TiN, the binding ability of high speed steel substrate storeroom excellence and good toughness.Accompany (TiN+CrN) layer as cushion of eliminating residualinternal stress between the TiN layer is with CrAlN, this structure improves the shock resistance of coating as far as possible, avoids coating breaking in use.
The specific embodiment
The invention will be further described below in conjunction with embodiment, need to prove, embodiment does not constitute the restriction to the claimed scope of the present invention.
The surface treatment of embodiment 1 carbide alloy rail processing blade
The preparation method of a kind of TiN/ (TiN+CrN)/CrAlN nano-composite coating comprises the steps and process conditions:
(1) to the surface preparation of carbide alloy rail processing cutter: blade is placed " brute force " board alkalinous metal cleaning fluid boil 40 minutes surface degreasings; Under the room temperature blade placed the ultrasonic processing of ultrasonic cleaning machine (frequency 40kHz) 10 minutes that fills the alkalinous metal cleaning fluid; Blade after cleaning is put into the straight alcohol solution dehydrates handle dry 60 minutes of the baking oven that is placed on 120 ℃.
(2) carbide alloy rail processing blade preheats: will pack in the BD 802 088 BE vacuum coating stoves of Balzers company production through pretreated blade, and vacuumize and reach 5 * 10
-3Behind the Pa, feed Ar gas, keeping vacuum is 2.3 * 10
-1Pa starts auxiliary auxiliary resistance heater in HCD electron gun and the body of heater.After the HCD electron gun produced direct-current arc, control HCD electron gun current was 150A; The direct-current arc direct irradiation workpiece of HCD electron gun.The final vacuum indoor temperature was 191 ℃ in 20 minutes.
(3) carbide alloy rail processing blade face etching: vacuum remains unchanged (only feeding Ar gas), and vacuum degree in vacuum chamber is 2.3 * 10
-1Pa.Adjusting the HCD electron gun current is 150A.Start some negative electrodes multi sphere titanium target in the following order successively, target current 73A, and workpiece applied bias voltage: start 1 negative electrode multi sphere titanium target earlier, workpiece is applied the 800V pulsed bias, close after applying 4 minutes; Start 2 negative electrode multi sphere titanium targets, workpiece is applied the 600V bias voltage, close after applying 6 minutes thereafter; Restart 1 negative electrode multi sphere titanium target, workpiece is applied the 600V bias voltage, close after applying 6 minutes; Start 2 negative electrode multi sphere titanium targets at last, workpiece is applied the 400V bias voltage, apply 12 minutes.Clean and finish 258 ℃ of plated film stove vacuum indoor temperatures.
(4) transition zone preparation process: close the negative electrode multi sphere titanium target of cleaning step, keep HCD electron gun direct-current arc size of current and still be 150A, feed N
2Increase room pressure to 2.6 * 10
-1Pa; Focus on HCD electron gun direct-current arc in crucible 5 minutes.Close the HCD electron gun afterwards, close the Ar source of the gas.Regulate N
2Throughput, keeping the pressure of plated film stove vacuum chamber is 1Pa, in the following order starter cathode multi sphere titanium target successively, target current is 85A, and workpiece applied bias voltage: start 2 negative electrode multi sphere titanium targets earlier, workpiece is applied the 400V pulsed bias, close after applying 4 minutes; Start 2 negative electrode multi sphere titanium targets subsequently, workpiece is applied the 300V pulsed bias, apply 12 minutes.
(5) (TiN+CrN) nano composite multiple layer preparation: regulate N
2Flux, keeping plated film stove vacuum indoor pressure is 0.5 * 10
-1Pa.Adjust workpiece bias in the following order successively, start the negative electrode multi sphere titanium target (being called for short the titanium target) and the negative electrode multi sphere chromium target (being called for short the chromium target) of equal number, target current is 80A: start earlier 1 titanium target and 1 chromium target, workpiece is applied the 200V pulsed bias, close after applying 6 minutes; Start 2 titanium targets and 2 chromium targets subsequently, workpiece is applied the 150V pulsed bias, apply 8 minutes.
(6) CrAlN nano composite multiple layer preparation: only feed N
2, keeping vacuum indoor pressure is 0.4 * 10
-1Pa.Adjust workpiece bias in the following order and start the negative electrode multi sphere CrAl alloys target of some that (composition is Cr
40Al
60), target current 87A: start earlier 2 negative electrode multi sphere CrAl alloys target, workpiece is applied the 150V pulsed bias, close after applying 15 minutes; Start 3 negative electrode multi sphere CrAl alloys target subsequently, workpiece is applied the 120V pulsed bias, close after applying 15 minutes; Restart 4 negative electrode multi sphere CrAl alloys target, workpiece is applied the 100V pulsed bias, apply 15 minutes.The vacuum chamber temperature was 312 ℃ when coating finished.
Gained appearance of coat gray, the gross thickness of ball milling vestige testing coating are 3.2 μ m; NANO mechanics probing needle testing coating hardness is 36.1GPa, acoustic emission scratching instrument testing coating adhesion 70N.
Embodiment 2 cold work die steel SKD1 alloy substrates surface treatments
Experiment is cut into the rectangle sample of 10 * 10 * 20 (mm) with SKD1 trade mark alloy (Rockwell hardness is HRC63 after the quenching+temper), and will be wherein simultaneously through grinding, polishing, so that test correlated performance after coating TiN/ (TiN+CrN)/CrAlN nano-composite coating.
(1) surface preparation of SKD1 alloy sample: sample is placed " powerful board " alkalinous metal cleaning fluid boil 10 minutes surface degreasings; Under the room temperature sample placed ultrasonic 8 minutes of the ultrasonic cleaning machine (frequency 40kHz) that fills the alkalinous metal cleaning fluid; Blade after cleaning is put into the straight alcohol solution dehydrates handle dry 30 minutes of the baking oven that is placed on 120 ℃.
(2) the SKD1 alloy sample preheats: will pack in the BD 802088 BE vacuum coating stoves that Balzers company produces through pretreated sample, and vacuumize and reach 5 * 10
-3Behind the Pa, feed Ar gas, keeping vacuum is 2.3 * 10
-1Pa starts the HCD electron gun.After the HCD electron gun produced direct-current arc, control HCD electron gun current was 110A; The direct-current arc direct irradiation sample of HCD electron gun.The final vacuum indoor temperature was 107 ℃ in 30 minutes.
(3) SKD1 alloy sample surface clean etching: vacuum remains unchanged (only feeding Ar), and vacuum degree in vacuum chamber is 2.3 * 10
-1Pa.Adjusting the HCD electron gun current is 120A.Start some negative electrodes multi sphere titanium target in the following order successively, target current 70A, and workpiece applied bias voltage: start 1 negative electrode multi sphere titanium target earlier, workpiece is applied the 600V pulsed bias, close after applying 8 minutes; Start 2 negative electrode multi sphere titanium targets, workpiece is applied the 500V bias voltage, close after applying 8 minutes thereafter; Restart 2 negative electrode multi sphere titanium targets, workpiece is applied the 400V bias voltage, close after applying 15 minutes; Start 2 negative electrode multi sphere titanium targets at last, workpiece is applied the 300V bias voltage, apply 15 minutes.Clean and finish 174 ℃ of vacuum indoor temperatures.
(4) transition zone preparation process: close the negative electrode multi sphere titanium target of cleaning step, keep Ar feeding amount in the step (2), keep HCD electron gun direct-current arc size of current and still be 120A, feed N
2Increase room pressure to 3.3 * 10
-1Pa; Focus on HCD electron gun direct-current arc in crucible 5 minutes.Close the HCD electron gun afterwards, close the Ar source of the gas.Regulate N
2Flow, keeping the pressure of plated film stove vacuum chamber is 1.5Pa, in the following order starter cathode multi sphere titanium target successively, negative electrode multi sphere titanium target current 80A, and workpiece applied bias voltage: start 2 negative electrode multi sphere titanium targets earlier, workpiece is applied the 400V pulsed bias, close after applying 2 minutes; Start 2 negative electrode multi sphere titanium targets, workpiece is applied the 300V bias voltage, apply 10 minutes thereafter.
(5) (TiN+CrN) nano composite multiple layer preparation: regulate N
2Flux, keeping plated film stove vacuum indoor pressure is 1Pa.Adjust workpiece bias in the following order successively, start the negative electrode multi sphere titanium target (being called for short the titanium target) and the negative electrode multi sphere chromium target (being called for short the chromium target) of equal number, target current is 70A: start earlier 1 titanium target and 1 chromium target, workpiece is applied the 200V pulsed bias, close after applying 6 minutes; Start 2 titanium targets and 2 chromium targets subsequently, workpiece is applied the 150V pulsed bias, apply 6 minutes.
(6) CrAlN nano composite multiple layer preparation: only feed N
2, the maintenance vacuum indoor pressure is 1Pa.Adjust workpiece bias in the following order and start the negative electrode multi sphere CrAl alloys target of some that (composition is Cr
40Al
60), target current 80A: start earlier 2 negative electrode multi sphere CrAl alloys target, workpiece is applied the 150V pulsed bias, close after applying 5 minutes; Start 3 negative electrode multi sphere CrAl alloys target subsequently, workpiece is applied the 120V pulsed bias, close after applying 10 minutes; Restart 4 negative electrode multi sphere CrAl alloys target, workpiece is applied the 100V pulsed bias, apply 15 minutes.Plated film stove vacuum chamber temperature was 194 ℃ when coating finished.
Gained appearance of coat gray, the gross thickness of ball milling vestige testing coating are 2.1 μ m; NANO mechanics probing needle testing coating hardness is 31.7GPa, acoustic emission scratching instrument testing coating adhesion 63N.
Embodiment 3 high-speed steel (SKH51) milling cutter and test piece face coat are handled
The milling cutter material trademark is SKH51, put into the rectangle sample (Rockwell hardness is HRC65 after the quenching+temper) of 10 * 10 * 20 (mm) with same heat treating regime during surface treatment with stove, and with the one side of sample through grind, polishing so that test correlated performance after coating TiN/ (TiN+CrN)/CrAlN nano-composite coating.
(1) workpiece and sample surfaces preliminary treatment: pending workpiece, sample are placed " powerful board " alkalinous metal cleaning fluid boil 120 minutes surface degreasings (milling cutter surface oil stain is serious); Under the room temperature workpiece, sample placed ultrasonic 15 minutes of the ultrasonic cleaning machine (frequency 40kHz) that fills the alkalinous metal cleaning fluid; Workpiece, sample after cleaning are put into straight alcohol solution to be taken off and handles dry 30 minutes of the baking oven that is placed on 120 ℃.
(2) preheat: will pack in the BD 802 088 BE vacuum coating stoves that Balzers company produces through pretreated workpiece, sample, and vacuumize and reach 5 * 10
-3Behind the Pa, feed Ar gas, keeping vacuum is 4 * 10
-1Pa starts the HCD electron gun.After the HCD electron gun produced direct-current arc, control HCD electron gun current was 180A; The direct-current arc direct irradiation sample of HCD electron gun.The final vacuum indoor temperature was 112 ℃ in 15 minutes.
(3) workpiece and sample surfaces etching: vacuum remains unchanged (only feeding Ar), and vacuum degree in vacuum chamber is 4 * 10
-1Pa, the HCD electron gun current still remains 180A.Start some negative electrodes multi sphere titanium target target current 80A in the following order successively, and workpiece is applied bias voltage: start earlier 1 negative electrode multi sphere titanium target, workpiece is applied the 600V pulsed bias, close after applying 5 minutes; Start 2 negative electrode multi sphere titanium targets, workpiece is applied the 500V bias voltage, close after applying 5 minutes thereafter; Restart 2 negative electrode multi sphere titanium targets, workpiece is applied the 400V bias voltage, close after applying 10 minutes; Start 2 negative electrode multi sphere titanium targets at last, workpiece is applied the 300V bias voltage, apply 10 minutes.Clean and finish 187 ℃ of vacuum indoor temperatures.
(4) transition zone preparation process: close the negative electrode multi sphere titanium target of cleaning step, keep Ar feeding amount in the step (2), keep HCD electron gun direct-current arc size of current and still be 180A, feed N
2Increase room pressure to 4.3 * 10
-1Pa; Focus on HCD electron gun direct-current arc in crucible 5 minutes.Close the HCD electron gun afterwards, close the Ar source of the gas.Regulate N
2Flow, keeping the pressure of plated film stove vacuum chamber is 0.5Pa, in the following order starter cathode multi sphere titanium target successively, negative electrode multi sphere titanium target current 90A, and workpiece applied bias voltage: start 2 negative electrode multi sphere titanium targets earlier, workpiece is applied the 400V pulsed bias, close after applying 2 minutes; Start 2 negative electrode multi sphere titanium targets, workpiece is applied the 300V bias voltage, apply 8 minutes thereafter.
(5) (TiN+CrN) nano composite multiple layer preparation: regulate N
2Flux, keeping plated film stove vacuum indoor pressure is 0.5Pa.Adjust workpiece bias in the following order successively, start the negative electrode multi sphere titanium target (being called for short the titanium target) and the negative electrode multi sphere chromium target (being called for short the chromium target) of equal number, target current is 80A: start earlier 1 titanium target and 1 chromium target, workpiece is applied the 200V pulsed bias, close after applying 12 minutes; Start 2 titanium targets and 2 chromium targets subsequently, workpiece is applied the 150V pulsed bias, apply 12 minutes.
(6) CrAlN nano composite multiple layer preparation: only feed N
2, the maintenance vacuum indoor pressure is 0.5Pa.Adjust workpiece bias in the following order and start the negative electrode multi sphere CrAl alloys target of some that (composition is Cr
40Al
60), target current 90A: start earlier 2 negative electrode multi sphere CrAl alloys target, workpiece is applied the 150V pulsed bias, close after applying 10 minutes; Start 3 negative electrode multi sphere CrAl alloys target subsequently, workpiece is applied the 120V pulsed bias, close after applying 15 minutes; Restart 4 negative electrode multi sphere CrAl alloys target, workpiece is applied the 100V pulsed bias, apply 15 minutes.Plated film stove vacuum chamber temperature was 269 ℃ when coating finished.
Gained appearance of coat gray, the gross thickness of ball milling vestige testing coating are 4.7 μ m; NANO mechanics probing needle testing coating hardness is 33.6GPa, acoustic emission scratching instrument testing coating adhesion 71N.
Claims (7)
1. a TiN/ (TiN+CrN)/CrAlN nano-composite coating, it is characterized in that: this nanocomposite laminated coating is to be on the instrument or die matrix of carbide alloy, high-speed steel, refractory steel in material, and forming structure by transition zone TIN film, (TiN+CrN) nano composite multiple layer and CrAlN nano composite multiple layer successively is TiN/ (TiN+CrN)/Ti (CN) multiple layer metal nitride ceramics coating.
2. require the preparation method of described TiN/ (TiN+CrN)/CrAlN nano-composite coating according to right 1, it is characterized in that comprising the steps and process conditions:
(1) instrument or die surface preliminary treatment: place the alkalinous metal cleaning fluid to boil on instrument or mould and carry out surface degreasing; Under the room temperature instrument or mould are placed the ultrasonic processing of ultrasonic cleaning machine that fills the alkalinous metal cleaning fluid; Instrument after will cleaning then or mould are put into the straight alcohol solution dehydrates and are handled the back drying;
(2) preheat: will pack in the reacting furnace through pretreated instrument or mould, and vacuumize and reach 5x10
-3Behind the Pa, feed Ar gas, keeping vacuum is 1-4x10
-1Pa starts HCD electron gun and body of heater inner heating device; After the starting the arc of HCD electron gun, control HCD electron gun current is 110-180A; The direct-current plasma arc direct irradiation surface of the work in HCD electron gun source reaches 100 ℃-200 ℃ up to the vacuum indoor temperature;
(3) surface clean etching: it is 1-4x10 that feeding Ar gas is kept indoor vacuum
-1Pa, adjusting the HCD electron gun current is 120-180A; Workpiece is applied the 300-800V pulsed bias, starter cathode multi sphere titanium target, the titanium ion that sputters out bombards surface of the work under electric field action; Cleaning and lithography tool or die surface under high energy electron and metal ion acting in conjunction; Etching instrument or mould 30-60 minute, the vacuum indoor temperature was no more than 300 ℃;
(4) transition zone preparation: close the negative electrode multi sphere titanium target that step (2) is started, keep Ar gas feeding amount in the step (2), regulate N
2Gas feeding amount makes plated film stove vacuum chamber pressure be increased to 1.1-5x10
-1Pa; Focus on HCD electron gun direct-current arc in crucible, the HCD electron gun current is 130-180A; Close the HCD electron gun after pure titanium 3-7 minute in the evaporation crucible, close the Ar source of the gas; Regulate N
2Flow, the maintenance vacuum pressure is 0.5-1.5Pa, and workpiece applies the 300-400V bias voltage, starts at least 2 negative electrode multi sphere titanium targets, and target current is 80-90A; Adopt negative electrode multi sphere titanium target to coat 10-20 minute;
(5) (TiN+CrN) nano composite multiple layer preparation: close negative electrode multi sphere titanium target in the step (3); Regulate N
2Flux, the maintenance vacuum indoor pressure is 2.0-10x10
-1Pa; Adjust workpiece bias, start 1 negative electrode multi sphere titanium target and 1 negative electrode multi sphere chromium target earlier, workpiece is applied the 200V pulsed bias, close after applying 6-12 minute, target current is 70-80A; Restart 2 negative electrode multi sphere titanium targets and 2 negative electrode multi sphere chromium targets, workpiece is applied the 150V bias voltage, close after applying 6-12 minute, target current is 70-80A;
(6) CrAlN nano composite multiple layer preparation: only feed N
2, the maintenance vacuum indoor pressure is 1.0-10x10
-1Pa; The adjustment workpiece bias is 100-150V, starts at least 2 negative electrode multi sphere CrAl alloys target, and target current is 80-90A, is coated with time 20-40 minute, makes the thickness of whole TiN/ (TiN+CrN)/CrAlN nano-composite coating reach 1-5 μ m; The vacuum chamber temperature was lower than 400 ℃ when coating finished; By weight, the Al composition accounts for 50-70% in the target of described negative electrode multi sphere CrAl alloys target.
3. the preparation method of TiN/ according to claim 2 (TiN+CrN)/CrAlN nano-composite coating is characterized in that: the described vacuum of step (2) is 2.3x10
-1Pa; The HCD electron gun current is 130-160A.
4. the preparation method of TiN/ according to claim 2 (TiN+CrN)/CrAlN nano-composite coating is characterized in that: the described vacuum of step (3) is 2.3x10
-1Pa.
5. the preparation method of TiN/ according to claim 2 (TiN+CrN)/CrAlN nano-composite coating is characterized in that: the described increase room pressure of step (4) is to 2.5-4.1x10
-1Pa; The HCD electron gun current is 150A; Pure titanium is closed the HCD electron gun in the evaporation crucible after 5 minutes.
6. the preparation method of TiN/ according to claim 2 (TiN+CrN)/CrAlN nano-composite coating is characterized in that: it is 0.3-0.5x10 that step (5) keeps vacuum indoor pressure
-1Pa.
7. the preparation method of TiN/ according to claim 2 (TiN+CrN)/CrAlN nano-composite coating is characterized in that: it is 0.3-0.5x10 that step (6) keeps vacuum indoor pressure
-1Pa; The CrAl alloy target material is Cr
40Al
60Whole coating layer thickness is 2-3.5 μ m.
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| CN102787300A (en) * | 2011-05-18 | 2012-11-21 | 中国核动力研究设计院 | Cr/CrAlN gradient coating technology of supercritical water-cooled reactor fuel can surface |
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| ATE509139T1 (en) * | 2001-03-30 | 2011-05-15 | Hitachi Metals Ltd | COATED CUTTING TOOL FOR WARM/HOT FORMING |
| DE102004010285A1 (en) * | 2004-03-03 | 2005-09-29 | Walter Ag | Coating for a cutting tool and manufacturing process |
| CN100385038C (en) * | 2005-11-28 | 2008-04-30 | 吴大维 | Nano superhard composite film tool with high adhesion and its deposition method |
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