CN103789723B - A kind of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating and preparation method thereof - Google Patents

A kind of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating and preparation method thereof Download PDF

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CN103789723B
CN103789723B CN201410033859.2A CN201410033859A CN103789723B CN 103789723 B CN103789723 B CN 103789723B CN 201410033859 A CN201410033859 A CN 201410033859A CN 103789723 B CN103789723 B CN 103789723B
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coating
crn
preparation
cutter
coated
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CN103789723A (en
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赵海波
杜昊
王芳
梁红樱
鲜广
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Sichuan University
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Sichuan University
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Abstract

Cr/CrN/ (Ti, Al, Si disclosed by the invention, Cr) preparation method of N rigid composite coating comprises pre-treatment, heating, plasma clean, preparation Cr adhesion layer, preparation CrN transition layer and preparation (Ti, Al, Si, Cr) step such as N wearing layer.MF reactive magnetron sputtering technology is strengthened owing to have employed plasma in preparation method provided by the invention, thus the ionization level of target has been increased substantially, the nano-hardness improvement of the rigid composite coating of preparation is made to reach more than 34GPa, film-substrate cohesion grade is the HF1-HF2 of German standard VDI3198, therefore be particularly suitable for making the coating for high-speed dry type cutting stainless steel, iron-base superalloy, High Strength Construction Steel and wearable cast steel cutter, and coating process is simple, is more suitable for suitability for industrialized production.

Description

A kind of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating and preparation method thereof
Technical field
The invention belongs to tool surface composite coating material and preparing technical field thereof, be specifically related to a kind of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating and preparation method thereof, coating nano hardness prepared by the method can reach more than 34Gpa, and film-substrate cohesion grade is HF1 ~ HF2 (German standard VDI3198), is particularly suitable as the top coat of high-speed dry type cutting stainless steel, iron-base superalloy, High Strength Construction Steel and wearable cast steel cutter.
Background technology
Along with developing rapidly of industry, the cated cutter of Surface coating is widely used in material and cuts field.Research shows, has hardness and wear resistance is high, the feature that resistance of oxidation is strong containing cated cutter, can significantly improve cutting-tool's used life.But along with appearance and the development of high speed cutting and DRY CUTTING, common TiN and TiAlN coating has been difficult to meet the requirement of user to cutter coat work-ing life.
In order to improve the work-ing life of cutter coat, the new TiAlSiN coating researched and developed in recent years and TiAlCrN coating are successively applied to the cutter field of machining, wherein structure (the HaoDu of TiAlSiN coating, HaiboZhao, JiXiong, etal.Int.JournalofRefractoryMetalsandHardMaterials37 (2013) 60-66.) be amorphous Si 3n 4tissue encapsulation is around nano-TiAl N crystal grain, therefore coating can obtain very high hardness (46Gpa) and oxidation-resistance, but along with the increase of hardness, coating internal stress also has corresponding raising, bonding force between coating and cutter is caused to be deteriorated, therefore, TiAlSiN coating modal failure mode in cutting process is exactly that coating shedding lost efficacy.TiAlCrN coating (G.S.Fox-Rabinovich.SurfaceandCoatingsTechnology200 (2005) 1804-1813), though have higher oilness and oxidation-resistance, but its weave construction amorphous/nano crystal form, hardness low (30Gpa) is easy to produce wearing and tearing in cutting process.
Summary of the invention
The object of the invention is, for TiAlSiN coating and TiAlCrN coating Problems existing, to provide a kind of Cr/CrN/ (Ti, Al, Si, Cr) the N preparation method of rigid composite coating.
Another object of the present invention is to provide Cr/CrN/ (Ti, Al, Si, Cr) the N rigid composite coating of a kind of hardness of being prepared by aforesaid method and bonding force excellence.
The preparation method of Cr/CrN/ provided by the invention (Ti, Al, Si, Cr) N rigid composite coating, its processing step and condition as follows:
1), after cutter being loaded coating chamber, first at least to 5.0 × 10 are vacuumized to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 3.0 × 10 -1~ 4.5 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 140 ~ 180A, to cutter heating 40 ~ 150min;
2) at pressure 1.5 × 10 -1~ 2.0 × 10 -1under the argon shield of Pa, control cutter direct current (DC) bias-100 ~-200V, pulsed bias-500 ~-800V, then with the plasma body that the hot-cathode ion column arc that electric current is 110 ~ 160A produces, 15 ~ 50min is cleaned to cutter surface bombardment;
3) 8.0 × 10 -2~ 1.5 × 10 -1under the argon shield of Pa; it is made to evaporate with the hot-cathode ion column arc heating Cr ingot casting that electric current is 180 ~ 220A; and 5 ~ 10min is coated with to cutter makes it form one deck Cr adhesion layer on the surface, then passing into nitrogen, is 1 ﹕ 1.5 ~ 3 and 3.0 × 10 in the throughput ratio of argon gas and nitrogen -1~ 4.5 × 10 -1be coated with 15 ~ 30min under the pressure of Pa, make Cr adhesion layer surface form one deck CrN transition layer;
4) continuing by throughput ratio is the mixed gas that 1 ﹕ 1.5 ~ 3 passes into argon gas and nitrogen in coating chamber, makes pressure be 3.0 × 10 -1~ 4.5 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-40 ~-70V, hot-cathode ion column arc current is adjusted to 100 ~ 110A, open the control power supply of MF reactive magnetron sputtering simultaneously, and be coated with 120 ~ 180min under making the electric current of TiAlSiCr target remain on 4.0 ~ 7.0A, make the CrN transition layer surface of cutter form one deck (Ti again, Al, Si, Cr) N coating, then naturally cooling.
Above method TiAlSiCr target used is TixAlySizCr1-x-y-z composite alloy target, and its titanium aluminium silicochromium atomic ratio is 50 ~ 70:20 ~ 30:1 ~ 7:1 ~ 5, and preferably 65 ~ 70:20 ~ 28:1 ~ 6:1 ~ 4, purity is 99.99%.
Above method the 3rd) pressure preferably 8.0 × 10 that is coated with Cr adhesion layer in step -2~ 1.2 × 10 -1pa, the electric current preferably 200 ~ 220A of hot-cathode ion column arc, is coated with time preferably 5 ~ 7min.
Above method the 3rd) be coated with the argon gas of CrN transition layer and throughput ratio preferably 1 ﹕ 1.5 ~ 2.5 of nitrogen in step, pressure preferably 4.0 × 10 -1~ 4.5 × 10 -1pa, is coated with time preferably 15 ~ 25min.
Above method the 4th) be coated with (Ti, Al, Si in step, Cr) argon gas of N coating and nitrogen flow are than preferred 1 ﹕ 1.5 ~ 2.5, the electric current preferably 5.0 ~ 7.0A of preferred 105 ~ 110A, the TiAlSiCr target of hot-cathode ion column arc current, is coated with time preferably 120 ~ 160min.
TiAlSiCr target described in above method totally four pieces, and be placed on the inwall of coating chamber in mode facing each other.
Cr/CrN/ (the Ti prepared by aforesaid method provided by the invention, Al, Si, Cr) N rigid composite coating, this compound coating is three layers, Cr adhesion layer, CrN transition layer and (Ti is outwards followed successively by from tool surface, Al, Si, Cr) N coating, its nano hardness >=34Gpa, reaches the HF1 ~ HF2 of German standard VDI3198 with tool matrix bonding force grade.
In above-mentioned compound coating, the thickness of Cr adhesion layer is 50 ~ 200nm, the thickness of CrN transition layer is 100 ~ 500nm, (Ti, Al, Si, Cr) thickness of N coating is 2 ~ 5 μm, its weave construction is nanocrystalline structure, TiN(111 at X-ray diffraction) face diffracted intensity < 100, TiN (200) diffracted intensity >=300, face.
The present invention compared with prior art, has the following advantages:
1) MF reactive magnetron sputtering technology is strengthened owing to have employed plasma in preparation method provided by the invention, thus the ionization level of target has been increased substantially, not only make gained coating structure evenly, finer and close, and be also provided with higher bonding force with matrix cutter.
2) be that the TixAlySizCr1-x-y-z composite alloy target that purity reaches 99.99% carries out sputter coating due to what adopt in preparation method provided by the invention, thus the stability of obtained coating performance is made to be guaranteed, also reduce the complexity of coating process simultaneously, be more suitable for suitability for industrialized production.
3) owing to comprising Cr adhesion layer, CrN transition layer and (Ti, Al, Si in compound coating provided by the invention, Cr) N coating, and wherein Cr adhesion layer is not only better with the consistency of matrix, and also there is good diffustivity, effectively can improve the bonding force between coating and matrix cutter; CrN transition layer can reduce the difference of the thermal expansivity between Cr adhesion layer Yu (Ti, Al, Si, Cr) N coating, reduces the stress between each layer, makes coating obtain higher intensity; And (Ti, Al, Si, Cr) N coating is then because having higher hardness and lower Young's modulus, coating can be made to have better mechanical property, thus make compound coating nano hardness can >=34Gpa, there is better wear resistance, itself and tool matrix bonding force grade can be made again to reach the HF1 ~ HF2 of German standard VDI3198, longer service life simultaneously.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating fracture apperance prepared by the embodiment of the present invention 4.
Fig. 2 is the scanning electron microscope (SEM) photograph of Ti/TiN/TiAlN coating fracture apperance prepared by comparative example 1.
Fig. 3 is Ti/TiAlSiN coating fracture apperance scanning electron microscope (SEM) photograph prepared by comparative example 2.
Fig. 4 is Ti/TiN/TiAlCrN coating fracture apperance scanning electron microscope (SEM) photograph prepared by comparative example 3.
Fig. 5 is Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating and the tool matrix bonding force schematic diagram of the embodiment of the present invention 4 preparation.
Fig. 6 is Ti/TiN/TiAlN coating and the tool matrix bonding force schematic diagram of comparative example 1 preparation.
Fig. 7 is Ti/TiAlSiN coating and the tool matrix bonding force schematic diagram of comparative example 2 preparation.
Fig. 8 is Ti/TiN/TiAlCrN coating and the tool matrix bonding force schematic diagram of comparative example 3 preparation.
Fig. 9 is the XRD figure spectrum of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating prepared by the embodiment of the present invention 4.
Embodiment
Below by specific embodiment, the present invention is further illustrated, but protection content of the present invention is not limited to following examples.
What deserves to be explained is, 1) following examples TiAlSiCr target used is that the applicant customizes in Antai Science and Technology Co., Ltd.2) coating hardness of following examples and the cutter product prepared by comparative example adopts nanohardness tester MTSSystemsCorp., OakRidge, TN, USA, and by surperficial velocity of approach 10nm/s, the dark 200nm of minimum pressure, the dark 300nm condition of maximum pressure carries out testing.3) the bonding force grade of following examples and the coating prepared by comparative example and cutter adopts Rockwell hardometer HR-150A type, tests under the HRC diamond penetrator, load 60Kg of cone angle 120 °.4) thickness of each layer of compound coating is by scanning electron microscope (S300-N, Hitachi, Japan) observation test.
Embodiment 1
1) load coating chamber by carrying out the tungsten carbide tap after oil removing, sandblasting and ultrasonic cleaning by ordinary method, first 5.0 × 10 are evacuated to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 3.0 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 150A, to cutter heating 150min;
2) at pressure 1.8 × 10 -1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V, pulsed bias-700V, then cleans 30min with the plasma body that the hot-cathode ion column arc that electric current is 110A produces to cutter surface bombardment;
3) be 8.0 × 10 at pressure -2under Pa argon shield; it is made to evaporate with the hot-cathode ion column arc heating Cr ingot casting that electric current is 200A; and 10min is coated with to cutter makes it form one deck Cr adhesion layer on the surface, then passing into throughput ratio is the argon gas of 1:1.5 and the mixed gas of nitrogen, is 4.0 × 10 at pressure -1be coated with 15min under Pa, make Cr adhesion layer surface form one deck CrN transition layer;
4) be the mixed gas that 1 ﹕ 3 passes into argon gas and nitrogen in coating chamber by throughput ratio, keep pressure to be 3.0 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-40V, hot-cathode ion column arc current is adjusted to 105A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering: the composite alloy target of Al:Si:Cr=70:28:1:1 simultaneously, and be coated with 120min under making the electric current of TiAlSiCr target remain on 5.0A, make the CrN transition layer surface of cutter form one deck (Ti again, Al, Si, Cr) N coating, then naturally cooling.
This tungsten carbide tap applies Cr/CrN/ (Ti, Al, Si, Cr) recording hardness after N compound coating is 34 ~ 36Gpa, Cr adhesion layer, CrN transition layer and (Ti, Al, Si, Cr) thickness of N coating be respectively 100nm, 100nm, 2.3 μm, coating and tool matrix bonding force grade are HF2.
Embodiment 2
1) load coating chamber by carrying out the carbide-tipped lathe tool after oil removing, sandblasting and ultrasonic cleaning by ordinary method, first 5.0 × 10 are evacuated to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 4.0 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 160A, to cutter heating 100min;
2) at pressure 1.5 × 10 -1under the argon shield of Pa, controlling cutter direct current (DC) bias is-150V, pulsed bias-600V, then cleans 40min with the plasma body that the hot-cathode ion column arc that electric current is 120A produces to cutter surface bombardment;
3) be 1.0 × 10 at pressure -1under Pa argon shield; it is made to evaporate with the hot-cathode ion column arc heating Cr ingot casting that electric current is 180A; and 6min is coated with to cutter makes it form one deck Cr adhesion layer on the surface, then passing into throughput ratio is the argon gas of 1:3 and the mixed gas of nitrogen, is 3.0 × 10 at pressure -1be coated with 20min under Pa, make Cr adhesion layer surface form one deck CrN transition layer;
4) be the mixed gas that 1:2 passes into argon gas and nitrogen in coating chamber by throughput ratio, keep pressure to be 4.0 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-50V, hot-cathode ion column arc current is adjusted to 100A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering: the composite alloy target of Al:Si:Cr=60:30:6:4 simultaneously, and be coated with 140min under making the electric current of TiAlSiCr target remain on 4.0A, make the CrN transition layer surface of cutter form one deck (Ti again, Al, Si, Cr) N coating, then naturally cooling.
This carbide-tipped lathe tool applies Cr/CrN/ (Ti, Al, Si, Cr) recording hardness after N compound coating is 38 ~ 40Gpa, Cr adhesion layer, CrN transition layer and (Ti, Al, Si, Cr) thickness of N coating be respectively 60nm, 200nm, 2.5 μm, coating and tool matrix bonding force grade are HF1.
Embodiment 3
1) load coating chamber by carrying out the inserted drill after oil removing, sandblasting and ultrasonic cleaning by ordinary method, first 5.0 × 10 are evacuated to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 3.0 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 140A, to cutter heating 40min;
2) at pressure 1.5 × 10 -1under the argon shield of Pa, controlling cutter direct current (DC) bias is-100V, pulsed bias-500V, then cleans 15min with the plasma body that the hot-cathode ion column arc that electric current is 110A produces to cutter surface bombardment;
3) be 1.2 × 10 at pressure -1under Pa argon shield; it is made to evaporate with the hot-cathode ion column arc heating Cr ingot casting that electric current is 210A; and 7min is coated with to cutter makes it form one deck Cr adhesion layer on the surface, then passing into throughput ratio is the argon gas of 1:2.5 and the mixed gas of nitrogen, is 4.2 × 10 at pressure -1be coated with 30min under Pa, make Cr adhesion layer surface form one deck CrN transition layer;
4) be the mixed gas that 1 ﹕ 1.5 passes into argon gas and nitrogen in coating chamber by throughput ratio, keep pressure to be 3.5 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-60V, hot-cathode ion column arc current is adjusted to 110A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering: the composite alloy target of Al:Si:Cr=70:20:5:5 simultaneously, and be coated with 160min under making the electric current of TiAlSiCr target remain on 7.0A, make the CrN transition layer surface of cutter form one deck (Ti again, Al, Si, Cr) N coating, then naturally cooling.
This inserted drill applies Cr/CrN/ (Ti, Al, Si, Cr) recording hardness after N compound coating is 32 ~ 35Gpa, Cr adhesion layer, CrN transition layer and (Ti, Al, Si, Cr) thickness of N coating be respectively 89nm, 500nm, 5.0 μm, coating and tool matrix bonding force grade are HF1.
Embodiment 4
1) load coating chamber by carrying out the carbide-tipped milling cutter after oil removing, sandblasting and ultrasonic cleaning by ordinary method, first 5.0 × 10 are evacuated to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 4.5 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 180A, to cutter heating 80min;
2) at pressure 2.0 × 10 -1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V, pulsed bias-800V, then cleans 50min with the plasma body that the hot-cathode ion column arc that electric current is 160A produces to cutter surface bombardment;
3) be 1.5 × 10 at pressure -1under Pa argon shield; it is made to evaporate with the hot-cathode ion column arc heating Cr ingot casting that electric current is 220A; and 5min is coated with to cutter makes it form one deck Cr adhesion layer on the surface, then passing into throughput ratio is the argon gas of 1:2.0 and the mixed gas of nitrogen, is 4.5 × 10 at pressure -1be coated with 25min under Pa, make Cr adhesion layer surface form one deck CrN transition layer;
4) be the mixed gas that 1 ﹕ 2.5 passes into argon gas and nitrogen in coating chamber by throughput ratio, keep pressure to be 4.5 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-70V, hot-cathode ion column arc current is adjusted to 110A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering: the composite alloy target of Al:Si:Cr=65:25:7:3 simultaneously, and be coated with 180min under making the electric current of TiAlSiCr target remain on 6.0A, make the CrN transition layer surface of cutter form one deck (Ti again, Al, Si, Cr) N coating, then naturally cooling.
This carbide-tipped milling cutter applies Cr/CrN/ (Ti, Al, Si, Cr) recording hardness after N compound coating is 34 ~ 41Gpa, Cr adhesion layer, CrN transition layer and (Ti, Al, Si, Cr) thickness of N coating be respectively 50nm, 350nm, 2.0 μm, coating and tool matrix bonding force grade are HF1.
Comparative example 1
1) load coating chamber by carrying out the carbide-tipped milling cutter after oil removing, sandblasting and ultrasonic cleaning by ordinary method, first 5.0 × 10 are evacuated to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 4.5 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 180A, to cutter heating 80min;
2) at pressure 2.0 × 10 -1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V, pulsed bias-800V, then cleans 50min with the plasma body that the hot-cathode ion column arc that electric current is 160A produces to cutter surface bombardment;
3) be 1.5 × 10 at pressure -1under the argon shield of Pa; it is made to evaporate with the hot-cathode ion column arc heating Ti ingot casting that electric current is 220A; and 5min is coated with to cutter makes it form one deck Ti adhesion layer on the surface, then passing into throughput ratio is the argon gas of 1:2 and the mixed gas of nitrogen, is 4.5 × 10 at pressure -1be coated with 25min under Pa, make Ti adhesion layer surface form one deck TiN transition layer;
4) be the mixed gas that 1 ﹕ 2.5 passes into argon gas and nitrogen in coating chamber by throughput ratio, keep pressure to be 4.5 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-70V, hot-cathode ion column arc current is adjusted to 110A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering: the composite alloy target of Al=50:50 simultaneously, and be coated with 180min under making the electric current of TiAl target remain on 6.0A, the TiN transition layer surface of cutter is made to form one deck TiAlN coating again, then naturally cooling.
Comparative example 2
1) load coating chamber by carrying out the carbide-tipped milling cutter after oil removing, sandblasting and ultrasonic cleaning by ordinary method, first 5.0 × 10 are evacuated to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 4.5 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 180A, to cutter heating 80min;
2) at pressure 2.0 × 10 -1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V, pulsed bias-800V, then cleans 50min with the plasma body that the hot-cathode ion column arc that electric current is 160A produces to cutter surface bombardment;
3) be 1.5 × 10 at pressure -1under Pa argon shield, make it evaporate with the hot-cathode ion column arc heating Ti ingot casting that electric current is 220A, and 5min is coated with to cutter makes it form one deck Ti transition layer on the surface;
4) be the mixed gas that 1 ﹕ 2.5 passes into argon gas and nitrogen in coating chamber by throughput ratio, keep pressure to be 4.5 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-70V, hot-cathode ion column arc current is adjusted to 110A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering: the composite alloy target of Al:Si=60:30:10 simultaneously, and be coated with 180min under making the electric current of TiAlSi target remain on 6.0A, the Ti transition layer surface of cutter is made to form one deck TiAlSiN coating again, then naturally cooling.
Comparative example 3
1) load coating chamber by carrying out the carbide-tipped milling cutter after oil removing, sandblasting and ultrasonic cleaning by ordinary method, first 5.0 × 10 are evacuated to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 4.5 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 180A, to cutter heating 80min;
2) at pressure 2.0 × 10 -1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V, pulsed bias-800V, then cleans 50min with the plasma body that the hot-cathode ion column arc that electric current is 160A produces to cutter surface bombardment;
3) be 1.5 × 10 at pressure -1under Pa argon shield; it is made to evaporate with the hot-cathode ion column arc heating Ti ingot casting that electric current is 220A; and 5min is coated with to cutter makes it form one deck Ti adhesion layer on the surface, then passing into throughput ratio is the argon gas of 1:2 and the mixed gas of nitrogen, is 4.5 × 10 at pressure -1be coated with 25min under Pa, make Ti adhesion layer surface form one deck TiN transition layer;
4) be the mixed gas that 1 ﹕ 2.5 passes into argon gas and nitrogen in coating chamber by throughput ratio, keep pressure to be 4.5 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-70V, hot-cathode ion column arc current is adjusted to 110A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering: the composite alloy target of Al:Cr=20:70:10 simultaneously, and be coated with 180min under making the electric current of TiAlCr target remain on 6.0A, the TiN transition layer surface of cutter is made to form one deck TiAlCrN coating again, then naturally cooling.
In order to investigate gained compound coating of the present invention and comparative example cutter composite coating, the present invention has done following detection to it:
1) coating fracture apperance is observed
Adopt scanning electron microscope (S300-N, Hitachi, Japan) to carry out observation test to the embodiment of the present invention 4 and comparative example 1-3 gained coating fracture apperance, result is shown in Fig. 1,2,3,4 respectively.First Cr/CrN/ (Ti can be found out from Fig. 1, Al, Si, Cr) N rigid composite coating is fine and closely woven compared with Ti/TiN/TiAlN coating fractograph, secondly Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating fractograph is divided into three layers, outermost layer (Ti, Al, Si, Cr) N coating structure is crystalline state nanometer; The coating fracture apperance of Fig. 2 is typical column crystal, easily ruptures time this crystal is subject to transverse load; The coating of Fig. 3, without obvious columnar shape, have obvious interface, therefore bonding force is lower between coating and matrix; The coating of Fig. 4 is without column crystal form, and without sharp interface between matrix, this form hardness is lower, and toughness is higher.Therefore Cr/CrN/ of the present invention (Ti, Al, Si, Cr) N rigid composite coating is than having better mechanical property.
2) coating nano hardness test
Adopt nanohardness tester MTSSystemsCorp., OakRidge, TN, USA, by surperficial velocity of approach 10nm/s, the dark 200nm of minimum pressure, the dark 500nm condition of maximum pressure is tested the embodiment of the present invention and comparative example 1-3 gained coating.Wherein the test result of the embodiment of the present invention 4 and comparative example 1-3 gained coating sees the following form.Test result from table, the embodiment of the present invention 4 gained Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating has higher hardness and lower Young's modulus compared with Ti/TiN/TiAlN coating in comparative example 1; Ti/TiAlSiN coating hardness in comparative example 2 is higher, but Young's modulus is also higher; Ti/TiN/TiAlCrN coating in comparative example 3, hardness is lower, and Young's modulus is also lower.
Table
3) coating and basal body binding force are tested
Adopt Rockwell hardometer HR-150A type, at the HRC diamond penetrator of cone angle 120 °, under load 60Kg, the embodiment of the present invention 4 and comparative example 1-3 gained coating and basal body binding force are tested, the results are shown in Figure 5,6,7,8.Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating impression can be observed from Fig. 5 and not occur extensive obscission, only there is hair line, illustrate coating and tool matrix bonding force high, coating and tool matrix bonding force grade are HF1; Ti/TiN/TiAlN coating impression can be observed from Fig. 6 and occur extensive obscission, illustrate coating and tool matrix bonding force low, this coating and tool matrix bonding force grade are HF4; Ti/TiAlSiN coating impression can be observed from Fig. 7 and also occur extensive obscission, illustrate coating and tool matrix bonding force low, this coating and tool matrix bonding force grade are HF4; Ti/TiN/TiAlCrN coating impression can be observed without obviously coming off from Fig. 8, but crackle comparatively Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating is more obvious, this coating and tool matrix bonding force grade are HF2.
4) the XRD test of coating
Adopt DX-1000 type XRD equipment (Cu target) to carry out XRD test to Cr/CrN/ (Ti, Al, Si, Cr) the N rigid composite coating prepared by the present invention, the results are shown in Figure 5.The XRD figure spectrum TiN(111 of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating as seen from Figure 5) face diffracted intensity < 100, TiN (200) face diffracted intensity is 300.This illustrates that this coating has higher comprehensive mechanical property.

Claims (8)

1. the preparation method of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating, processing step and the condition of the method are as follows:
1), after cutter being loaded coating chamber, first at least to 5.0 × 10 are vacuumized to coating chamber -3pa, then passes into argon gas, makes total pressure in coating chamber be 3.0 × 10 -1~ 4.5 × 10 -1pa, opens hot-cathode ion column arc and makes its electric current be 140 ~ 180A, to cutter heating 40 ~ 150min;
2) at pressure 1.5 × 10 -1~ 2.0 × 10 -1under the argon shield of Pa, control cutter direct current (DC) bias-100 ~-200V, pulsed bias-500 ~-800V, then with the plasma body that the hot-cathode ion column arc that electric current is 110 ~ 160A produces, 15 ~ 50min is cleaned to cutter surface bombardment;
3) at pressure 8.0 × 10 -2~ 1.5 × 10 -1under the argon shield of Pa; it is made to evaporate with the hot-cathode ion column arc heating Cr ingot casting that electric current is 180 ~ 220A; and 5 ~ 10min is coated with to cutter makes it form one deck Cr adhesion layer on the surface, then passing into nitrogen, is 1 ﹕ 1.5 ~ 3 and 3.0 × 10 in the throughput ratio of argon gas and nitrogen -1~ 4.5 × 10 -1be coated with 15 ~ 30min under the pressure of Pa, make Cr adhesion layer surface form one deck CrN transition layer;
4) continuing by throughput ratio is the mixed gas that 1 ﹕ 1.5 ~ 3 passes into argon gas and nitrogen in coating chamber, makes pressure be 3.0 × 10 -1~ 4.5 × 10 -1pa, and cutter direct current (DC) bias is adjusted to-40 ~-70V, hot-cathode ion column arc current is adjusted to 100 ~ 110A, open the control power supply of MF reactive magnetron sputtering simultaneously, and be coated with 120 ~ 180min under making the electric current of TiAlSiCr target remain on 4.0 ~ 7.0A, make the CrN transition layer surface of cutter form one deck (Ti again, Al, Si, Cr) N coating, then naturally cooling.
2. the preparation method of Cr/CrN/ according to claim 1 (Ti, Al, Si, Cr) N rigid composite coating, the method the 4th) TiAlSiCr target used is Ti in step xal ysi zcr (1-X-Y-Z)composite alloy target, its titanium aluminium silicochromium atomic ratio is 50 ~ 70:20 ~ 30:1 ~ 7:1 ~ 5, and purity is 99.99%.
3. the preparation method of Cr/CrN/ according to claim 1 (Ti, Al, Si, Cr) N rigid composite coating, the method the 3rd) pressure that is coated with Cr adhesion layer in step is 8.0 × 10 -2~ 1.2 × 10 -1pa, the electric current of hot-cathode ion column arc is 200 ~ 220A, and the time of being coated with is 5 ~ 7min.
4. the preparation method of Cr/CrN/ according to claim 1 (Ti, Al, Si, Cr) N rigid composite coating, the method the 3rd) throughput ratio of argon gas and nitrogen that is coated with CrN transition layer in step is 1 ﹕ 1.5 ~ 2.5, pressure is 4.0 × 10 -1~ 4.5 × 10 -1pa, the time of being coated with is 15 ~ 25min.
5. Cr/CrN/ (the Ti according to claim 1 or 2 or 3 or 4, Al, Si, Cr) preparation method of N rigid composite coating, the method the 4th) be coated with (Ti in step, Al, Si, Cr) argon gas of N coating and nitrogen flow ratio be 1 ﹕ 1.5 ~ 2.5, hot-cathode ion column arc current is 105 ~ 110A, the electric current of TiAlSiCr target remains on 5.0 ~ 7.0A, and the time of being coated with is 120 ~ 160min.
6. the preparation method of Cr/CrN/ according to claim 2 (Ti, Al, Si, Cr) N rigid composite coating, the method the 4th) titanium aluminium silicochromium atomic ratio is 65 ~ 70:20 ~ 28:1 ~ 6:1 ~ 4 in step TiAlSiCr target used.
7. the preparation method of Cr/CrN/ according to claim 5 (Ti, Al, Si, Cr) N rigid composite coating, the method the 4th) titanium aluminium silicochromium atomic ratio is 65 ~ 70:20 ~ 28:1 ~ 6:1 ~ 4 in step TiAlSiCr target used.
8. Cr/CrN/ (the Ti prepared by method described in claim 1, Al, Si, Cr) N rigid composite coating, this rigid composite coating is three layers, Cr adhesion layer is outwards followed successively by from tool surface, CrN transition layer and (Ti, Al, Si, Cr) N coating, its nano hardness >=34Gpa, HF1 ~ the HF2 of German standard VDI3198 is reached with tool matrix bonding force grade, wherein the thickness of Cr adhesion layer is 50 ~ 200nm, the thickness of CrN transition layer is 100 ~ 500nm, (Ti, Al, Si, Cr) thickness of N coating is 2 ~ 5 μm, and (Ti, Al, Si, Cr) N coating texture is nanocrystalline structure, at TiN (111) the face diffracted intensity < 100 of X-ray diffraction, TiN (200) diffracted intensity >=300, face.
CN201410033859.2A 2014-01-24 2014-01-24 A kind of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating and preparation method thereof Expired - Fee Related CN103789723B (en)

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