CN103789723A - Cr/CrN/(Ti, Al, Si, Cr)N composite hard coating and preparation method thereof - Google Patents
Cr/CrN/(Ti, Al, Si, Cr)N composite hard coating and preparation method thereof Download PDFInfo
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- CN103789723A CN103789723A CN201410033859.2A CN201410033859A CN103789723A CN 103789723 A CN103789723 A CN 103789723A CN 201410033859 A CN201410033859 A CN 201410033859A CN 103789723 A CN103789723 A CN 103789723A
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Abstract
The invention discloses a preparation method of a Cr/CrN/(Ti, Al, Si, Cr)N composite hard coating. The preparation method comprises the steps of pretreatment, heating, plasma cleaning, Cr adhesion layer preparation, CrN transition layer preparation, (Ti, Al, Si, Cr)N anti-wearing layer preparation and the like. As a plasma enhanced intermediate frequency reaction magnetron sputtering technology is adopted in the preparation method provided by the invention, the ionization rate of a target material is substantially increased, so that the surface nano-hardness of the prepared composite hard coating can reach above 34 GPa, and the membrane base bonding force grade of the hard coating is HF1-HF2 of German Standard VDI3198. Therefore, the preparation method is suitable for preparation of the coating for high-speed dry-type cutting stainless steel, iron-based high-temperature alloy, high-strength constructional steel and anti-wearing cast steel cutters. The coating is simple in process and suitable for industrial production.
Description
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, more than coating nano hardness prepared by the method can reach 34Gpa, 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 coated cated cutter in surface is widely used in material cutting field.Research shows, has hardness and wear resistance is high, the feature that resistance of oxidation is strong, the work-ing life that can obviously improve cutter containing cated cutter.But along with appearance and the development of high speed cutting and DRY CUTTING, common TiN and TiAlN coating have been difficult to meet user to the cutter coat requirement in work-ing life.
In order to improve the work-ing life of cutter coat, the new TiAlSiN coating of research and development and TiAlCrN coating are successively applied to the cutter field of machining in recent years, the wherein structure of TiAlSiN coating (Hao Du, Haibo Zhao, Ji Xiong, et al.Int.Journal of Refractory Metals and Hard Materials37 (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, cause bonding force variation between coating and cutter, therefore, TiAlSiN coating modal failure mode in cutting process is exactly that coating shedding lost efficacy.TiAlCrN coating (G.S.Fox-Rabinovich.Surface and Coatings Technology200 (2005) 1804-1813), though there is 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 the problem for TiAlSiN coating and the existence of TiAlCrN coating, a kind of Cr/CrN/ (Ti, Al, Si, Cr) preparation method of N rigid composite coating is provided.
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 are as follows:
1) cutter is packed into after coating chamber, first coating chamber is vacuumized at least to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 3.0 × 10
-1～4.5 × 10
-1pa, it is 140～180A that unlatching hot-cathode ion column arc makes its electric current, 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, the plasma body that the hot-cathode ion column arc that then pulsed bias-500～-800V is 110～160A with electric current produces is to tool surface Bombardment and cleaning 15～50min;
3) 8.0 × 10
-2～1.5 × 10
-1under the argon shield of Pa; the hot-cathode ion column arc that is 180～220A with electric current heating Cr ingot casting makes its evaporation; and cutter is coated with to 5～10min makes the upper one deck Cr adhesion layer that forms in its surface, then pass into nitrogen, be 1 ﹕ 1.5～3 and 3.0 × 10 in the throughput ratio of argon gas and nitrogen
-1～4.5 × 10
-1under the pressure of Pa, be coated with 15～30min, make Cr adhesion layer surface form one deck CrN transition layer;
4) continuing by throughput ratio is 1 ﹕ 1.5～3 to the mixed gas that passes into argon gas and nitrogen in coating chamber, and making pressure is 3.0 × 10
-1～4.5 × 10
-1pa, and cutter direct current (DC) bias is adjusted into-40～-70V, hot-cathode ion column arc current is adjusted into 100～110A, open the control power supply of MF reactive magnetron sputtering simultaneously, and the electric current of TiAlSiCr target is remained under 4.0～7.0A be coated with 120～180min, make the CrN transition layer surface of cutter form again one deck (Ti, 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, preferably 65～70:20～28:1～6:1～4, and 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 preferably 200～220A of electric current of hot-cathode ion column arc, is coated with preferably 5～7min of time.
Above method the 3rd) be coated with the argon gas of CrN transition layer and preferably 1 ﹕ 1.5～2.5 of the throughput ratio of nitrogen in step, pressure preferably 4.0 × 10
-1～4.5 × 10
-1pa, is coated with preferably 15～25min of time.
Above method the 4th) be coated with (Ti, Al, Si in step, Cr) argon gas of N coating and preferably 1 ﹕ 1.5～2.5 of nitrogen flow ratio, preferably 105～110A of hot-cathode ion column arc current, preferably 5.0～7.0A of the electric current of TiAlSiCr target, is coated with preferably 120～160min of time.
Totally four of TiAlSiCr targets described in above method, and be placed in mode facing each other on the inwall of coating chamber.
Cr/CrN/ (the Ti being prepared by aforesaid method provided by the invention, Al, Si, Cr) N rigid composite coating, this compound coating is three layers, outwards be followed successively by Cr adhesion layer, CrN transition layer and (Ti from tool surface, Al, Si, Cr) N coating, its nano hardness >=34Gpa, reaches 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 μ m, its weave construction is nanocrystalline structure, at the TiN(111 of X-ray diffraction) face diffracted intensity < 100, TiN (200) face diffracted intensity >=300.
The present invention compared with prior art, has the following advantages:
1) owing to having adopted plasma to strengthen MF reactive magnetron sputtering technology in preparation method provided by the invention, thereby increase substantially the ionization level of target, not only make gained coating structure more evenly, finer and close, and also had higher bonding force with matrix cutter.
2) be that purity reaches 99.99% TixAlySizCr1-x-y-z composite alloy target and carries out sputter coating due to what adopt in preparation method provided by the invention, thereby the stability of obtained coating performance is guaranteed, also the complexity that has reduced coating process, is more suitable in suitability for industrialized production simultaneously.
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, can effectively improve the bonding force between coating and matrix cutter; CrN transition layer can reduce the difference of the thermal expansivity between Cr adhesion layer and (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 because having higher hardness and lower Young's modulus, can make coating there is better mechanical property, thus make compound coating nano hardness can >=34Gpa, there is better wear resistance, can make again itself and tool matrix bonding force grade reach 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) the N rigid composite coating fracture apperance prepared of the embodiment of the present invention 4.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Ti/TiN/TiAlN coating fracture apperance prepared of 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 tool matrix bonding force schematic diagram prepared by the embodiment of the present invention 4.
Fig. 6 is Ti/TiN/TiAlN coating and tool matrix bonding force schematic diagram prepared by comparative example 1.
Fig. 7 is Ti/TiAlSiN coating and tool matrix bonding force schematic diagram prepared by comparative example 2.
Fig. 8 is Ti/TiN/TiAlCrN coating and tool matrix bonding force schematic diagram prepared by comparative example 3.
Fig. 9 is the XRD figure spectrum of Cr/CrN/ (Ti, Al, Si, Cr) the N rigid composite coating prepared of 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 the prepared cutter product of following examples and comparative example adopts nanohardness tester MTS Systems Corp., Oak Ridge, TN, USA, by surperficial velocity of approach 10nm/s, the dark 200nm of minimum pressure, the dark 300nm condition of maximum pressure is tested.3) the bonding force grade of the prepared coating of following examples and comparative example and cutter adopts Rockwell hardometer HR-150A type, under the HRC diamond penetrator of 120 ° of cone angles, load 60Kg, tests.4) thickness of each layer of compound coating is by scanning electron microscope (S300-N, Hitachi, Japan) observation test.
Embodiment 1
1) by packing coating chamber into the tungsten carbide tap that ordinary method is carried out after oil removing, sandblasting and ultrasonic cleaning, first coating chamber is evacuated to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 3.0 × 10
-1pa, it is 150A that unlatching hot-cathode ion column arc makes its electric current, to cutter heating 150min;
2) at pressure 1.8 × 10
-1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V that the plasma body that the hot-cathode ion column arc that then pulsed bias-700V is 110A with electric current produces is to tool surface Bombardment and cleaning 30min;
3) be 8.0 × 10 at pressure
-2under Pa argon shield; the hot-cathode ion column arc that is 200A with electric current heating Cr ingot casting makes its evaporation; and cutter is coated with to 10min makes the upper one deck Cr adhesion layer that forms in its 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
-1under Pa, be coated with 15min, make Cr adhesion layer surface form one deck CrN transition layer;
4) be 1 ﹕ 3 to the mixed gas that passes into argon gas and nitrogen in coating chamber by throughput ratio, keeping pressure is 3.0 × 10
-1pa, and by be adjusted into-40V of cutter direct current (DC) bias, hot-cathode ion column arc current is adjusted into 105A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering simultaneously: the composite alloy target of Al:Si:Cr=70:28:1:1, and the electric current of TiAlSiCr target is remained under 5.0A be coated with 120min, make the CrN transition layer surface of cutter form again one deck (Ti, Al, Si, Cr) N coating, then naturally cooling.
On this tungsten carbide tap, apply Cr/CrN/ (Ti, Al, Si, Cr) after N compound coating, recording hardness is 34～36Gpa, Cr adhesion layer, CrN transition layer and (Ti, Al, Si, Cr) thickness of N coating is respectively 100nm, 100nm, 2.3 μ m, and coating and tool matrix bonding force grade are HF2.
Embodiment 2
1) by packing coating chamber into the carbide-tipped lathe tool that ordinary method is carried out after oil removing, sandblasting and ultrasonic cleaning, first coating chamber is evacuated to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 4.0 × 10
-1pa, it is 160A that unlatching hot-cathode ion column arc makes its electric current, to cutter heating 100min;
2) at pressure 1.5 × 10
-1under the argon shield of Pa, controlling cutter direct current (DC) bias is-150V that the plasma body that the hot-cathode ion column arc that then pulsed bias-600V is 120A with electric current produces is to tool surface Bombardment and cleaning 40min;
3) be 1.0 × 10 at pressure
-1under Pa argon shield; the hot-cathode ion column arc that is 180A with electric current heating Cr ingot casting makes its evaporation; and cutter is coated with to 6min makes the upper one deck Cr adhesion layer that forms in its 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
-1under Pa, be coated with 20min, make Cr adhesion layer surface form one deck CrN transition layer;
4) be 1:2 to the mixed gas that passes into argon gas and nitrogen in coating chamber by throughput ratio, keeping pressure is 4.0 × 10
-1pa, and by be adjusted into-50V of cutter direct current (DC) bias, hot-cathode ion column arc current is adjusted into 100A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering simultaneously: the composite alloy target of Al:Si:Cr=60:30:6:4, and the electric current of TiAlSiCr target is remained under 4.0A be coated with 140min, make the CrN transition layer surface of cutter form again one deck (Ti, Al, Si, Cr) N coating, then naturally cooling.
On this carbide-tipped lathe tool, apply Cr/CrN/ (Ti, Al, Si, Cr) after N compound coating, recording hardness is 38～40Gpa, Cr adhesion layer, CrN transition layer and (Ti, Al, Si, Cr) thickness of N coating is respectively 60nm, 200nm, 2.5 μ m, and coating and tool matrix bonding force grade are HF1.
Embodiment 3
1) by packing coating chamber into the inserted drill that ordinary method is carried out after oil removing, sandblasting and ultrasonic cleaning, first coating chamber is evacuated to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 3.0 × 10
-1pa, it is 140A that unlatching hot-cathode ion column arc makes its electric current, to cutter heating 40min;
2) at pressure 1.5 × 10
-1under the argon shield of Pa, controlling cutter direct current (DC) bias is-100V that the plasma body that the hot-cathode ion column arc that then pulsed bias-500V is 110A with electric current produces is to tool surface Bombardment and cleaning 15min;
3) be 1.2 × 10 at pressure
-1under Pa argon shield; the hot-cathode ion column arc that is 210A with electric current heating Cr ingot casting makes its evaporation; and cutter is coated with to 7min makes the upper one deck Cr adhesion layer that forms in its 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
-1under Pa, be coated with 30min, make Cr adhesion layer surface form one deck CrN transition layer;
4) be 1 ﹕ 1.5 to the mixed gas that passes into argon gas and nitrogen in coating chamber by throughput ratio, keeping pressure is 3.5 × 10
-1pa, and by be adjusted into-60V of cutter direct current (DC) bias, hot-cathode ion column arc current is adjusted into 110A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering simultaneously: the composite alloy target of Al:Si:Cr=70:20:5:5, and the electric current of TiAlSiCr target is remained under 7.0A be coated with 160min, make the CrN transition layer surface of cutter form again one deck (Ti, Al, Si, Cr) N coating, then naturally cooling.
On this inserted drill, apply Cr/CrN/ (Ti, Al, Si, Cr) after N compound coating, recording hardness is 32～35Gpa, Cr adhesion layer, CrN transition layer and (Ti, Al, Si, Cr) thickness of N coating is respectively 89nm, 500nm, 5.0 μ m, and coating and tool matrix bonding force grade are HF1.
Embodiment 4
1) by packing coating chamber into the carbide-tipped milling cutter that ordinary method is carried out after oil removing, sandblasting and ultrasonic cleaning, first coating chamber is evacuated to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 4.5 × 10
-1pa, it is 180A that unlatching hot-cathode ion column arc makes its electric current, to cutter heating 80min;
2) at pressure 2.0 × 10
-1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V that the plasma body that the hot-cathode ion column arc that then pulsed bias-800V is 160A with electric current produces is to tool surface Bombardment and cleaning 50min;
3) be 1.5 × 10 at pressure
-1under Pa argon shield; the hot-cathode ion column arc that is 220A with electric current heating Cr ingot casting makes its evaporation; and cutter is coated with to 5min makes the upper one deck Cr adhesion layer that forms in its 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
-1under Pa, be coated with 25min, make Cr adhesion layer surface form one deck CrN transition layer;
4) be 1 ﹕ 2.5 to the mixed gas that passes into argon gas and nitrogen in coating chamber by throughput ratio, keeping pressure is 4.5 × 10
-1pa, and by be adjusted into-70V of cutter direct current (DC) bias, hot-cathode ion column arc current is adjusted into 110A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering simultaneously: the composite alloy target of Al:Si:Cr=65:25:7:3, and the electric current of TiAlSiCr target is remained under 6.0A be coated with 180min, make the CrN transition layer surface of cutter form again one deck (Ti, Al, Si, Cr) N coating, then naturally cooling.
On this carbide-tipped milling cutter, apply Cr/CrN/ (Ti, Al, Si, Cr) after N compound coating, recording hardness is 34～41Gpa, Cr adhesion layer, CrN transition layer and (Ti, Al, Si, Cr) thickness of N coating is respectively 50nm, 350nm, 2.0 μ m, and coating and tool matrix bonding force grade are HF1.
Comparative example 1
1) by packing coating chamber into the carbide-tipped milling cutter that ordinary method is carried out after oil removing, sandblasting and ultrasonic cleaning, first coating chamber is evacuated to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 4.5 × 10
-1pa, it is 180A that unlatching hot-cathode ion column arc makes its electric current, to cutter heating 80min;
2) at pressure 2.0 × 10
-1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V that the plasma body that the hot-cathode ion column arc that then pulsed bias-800V is 160A with electric current produces is to tool surface Bombardment and cleaning 50min;
3) be 1.5 × 10 at pressure
-1under the argon shield of Pa; the hot-cathode ion column arc that is 220A with electric current heating Ti ingot casting makes its evaporation; and cutter is coated with to 5min makes the upper one deck Ti adhesion layer that forms in its 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
-1under Pa, be coated with 25min, make Ti adhesion layer surface form one deck TiN transition layer;
4) be 1 ﹕ 2.5 to the mixed gas that passes into argon gas and nitrogen in coating chamber by throughput ratio, keeping pressure is 4.5 × 10
-1pa, and by be adjusted into-70V of cutter direct current (DC) bias, hot-cathode ion column arc current is adjusted into 110A, open the control power supply sputtered with Ti of MF reactive magnetron sputtering: the composite alloy target of Al=50:50 simultaneously, and the electric current that makes TiAl target remains under 6.0A and is coated with 180min, make the TiN transition layer surface of cutter form again one deck TiAlN coating, then naturally cooling.
Comparative example 2
1) by packing coating chamber into the carbide-tipped milling cutter that ordinary method is carried out after oil removing, sandblasting and ultrasonic cleaning, first coating chamber is evacuated to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 4.5 × 10
-1pa, it is 180A that unlatching hot-cathode ion column arc makes its electric current, to cutter heating 80min;
2) at pressure 2.0 × 10
-1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V that the plasma body that the hot-cathode ion column arc that then pulsed bias-800V is 160A with electric current produces is to tool surface Bombardment and cleaning 50min;
3) be 1.5 × 10 at pressure
-1under Pa argon shield, the hot-cathode ion column arc that is 220A with electric current heating Ti ingot casting makes its evaporation, and cutter is coated with to 5min makes the upper one deck Ti transition layer that forms in its surface;
4) be 1 ﹕ 2.5 to the mixed gas that passes into argon gas and nitrogen in coating chamber by throughput ratio, keeping pressure is 4.5 × 10
-1pa, and by be adjusted into-70V of cutter direct current (DC) bias, hot-cathode ion column arc current is adjusted into 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 the electric current that makes TiAlSi target remains under 6.0A and is coated with 180min, make the Ti transition layer surface of cutter form again one deck TiAlSiN coating, then naturally cooling.
Comparative example 3
1) by packing coating chamber into the carbide-tipped milling cutter that ordinary method is carried out after oil removing, sandblasting and ultrasonic cleaning, first coating chamber is evacuated to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 4.5 × 10
-1pa, it is 180A that unlatching hot-cathode ion column arc makes its electric current, to cutter heating 80min;
2) at pressure 2.0 × 10
-1under the argon shield of Pa, controlling cutter direct current (DC) bias is-200V that the plasma body that the hot-cathode ion column arc that then pulsed bias-800V is 160A with electric current produces is to tool surface Bombardment and cleaning 50min;
3) be 1.5 × 10 at pressure
-1under Pa argon shield; the hot-cathode ion column arc that is 220A with electric current heating Ti ingot casting makes its evaporation; and cutter is coated with to 5min makes the upper one deck Ti adhesion layer that forms in its 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
-1under Pa, be coated with 25min, make Ti adhesion layer surface form one deck TiN transition layer;
4) be 1 ﹕ 2.5 to the mixed gas that passes into argon gas and nitrogen in coating chamber by throughput ratio, keeping pressure is 4.5 × 10
-1pa, and by be adjusted into-70V of cutter direct current (DC) bias, hot-cathode ion column arc current is adjusted into 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 the electric current that makes TiAlCr target remains under 6.0A and is coated with 180min, make the TiN transition layer surface of cutter form again one deck TiAlCrN coating, 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 respectively Fig. 1,2,3,4.First can find out Cr/CrN/ (Ti 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, when this crystal is subject to transverse load, easily ruptures; The coating of Fig. 3, without obvious columnar shape, has obvious interface, therefore bonding force is lower between coating and matrix; The coating of Fig. 4 is without column crystal form, and between matrix without sharp interface, this form hardness is lower, 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 MTS Systems Corp., Oak Ridge, 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 test
Adopt Rockwell hardometer HR-150A type, at the HRC diamond penetrator of 120 ° of cone angles, 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.Can observe Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating impression from Fig. 5 and not occur extensive obscission, only have hair line, illustrate that coating and tool matrix bonding force are high, coating and tool matrix bonding force grade are HF1; Can observe Ti/TiN/TiAlN coating impression from Fig. 6 and occur extensive obscission, illustrate that coating and tool matrix bonding force are low, this coating and tool matrix bonding force grade are HF4; Can observe Ti/TiAlSiN coating impression from Fig. 7 and also occur extensive obscission, illustrate that coating and tool matrix bonding force are low, this coating and tool matrix bonding force grade are HF4; Can observe Ti/TiN/TiAlCrN coating impression without obviously coming off from Fig. 8, but crackle is more obvious compared with Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating, this coating and tool matrix bonding force grade are HF2.
4) XRD of coating test
Adopt DX-1000 type XRD equipment (Cu target) to carry out XRD test to the prepared Cr/CrN/ of the present invention (Ti, Al, Si, Cr) N rigid composite coating, the results are shown in Figure 5.The XRD figure of Cr/CrN/ (Ti, Al, Si, Cr) N rigid composite coating spectrum TiN(111 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 (9)
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) cutter is packed into after coating chamber, first coating chamber is vacuumized at least to 5.0 × 10
-3pa, then passes into argon gas, and making total pressure in coating chamber is 3.0 × 10
-1～4.5 × 10
-1pa, it is 140～180A that unlatching hot-cathode ion column arc makes its electric current, 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, the plasma body that the hot-cathode ion column arc that then pulsed bias-500～-800V is 110～160A with electric current produces is to tool surface Bombardment and cleaning 15～50min;
3) at pressure 8.0 × 10
-2～1.5 × 10
-1under the argon shield of Pa; the hot-cathode ion column arc that is 180～220A with electric current heating Cr ingot casting makes its evaporation; and cutter is coated with to 5～10min makes the upper one deck Cr adhesion layer that forms in its surface, then pass into nitrogen, be 1 ﹕ 1.5～3 and 3.0 × 10 in the throughput ratio of argon gas and nitrogen
-1～4.5 × 10
-1under the pressure of Pa, be coated with 15～30min, make Cr adhesion layer surface form one deck CrN transition layer;
4) continuing by throughput ratio is 1 ﹕ 1.5～3 to the mixed gas that passes into argon gas and nitrogen in coating chamber, and making pressure is 3.0 × 10
-1～4.5 × 10
-1pa, and cutter direct current (DC) bias is adjusted into-40～-70V, hot-cathode ion column arc current is adjusted into 100～110A, open the control power supply of MF reactive magnetron sputtering simultaneously, and the electric current of TiAlSiCr target is remained under 4.0～7.0A be coated with 120～180min, make the CrN transition layer surface of cutter form again one deck (Ti, Al, Si, Cr) N coating, then naturally cooling.
2. Cr/CrN/ (Ti according to claim 1, Al, Si, Cr) preparation method of N rigid composite coating, the method the 4th) TiAlSiCr target used is TixAlySizCr1-x-y-z composite alloy target in step, 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, 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) be coated with the argon gas of CrN transition layer in step and the throughput ratio of nitrogen 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. according to the Cr/CrN/ (Ti described in 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 and the nitrogen flow ratio of N coating 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. a Cr/CrN/ (Ti who is prepared by method described in claim 1, Al, Si, Cr) N rigid composite coating, this rigid composite coating is three layers, outwards be followed successively by Cr adhesion layer, CrN transition layer and (Ti from tool surface, Al, Si, Cr) N coating, its nano hardness >=34Gpa, reaches HF1～HF2 of German standard VDI3198 with tool matrix bonding force grade.
9. Cr/CrN/ according to claim 8 (Ti, Al, Si, Cr) N rigid composite coating, in this rigid composite coating, the thickness of Cr adhesion layer is 50～200nm, and the thickness of CrN transition layer is 100～500nm, (Ti, Al, Si, Cr) thickness of N coating is 2～5 μ m, its weave construction is nanocrystalline structure, at the TiN(111 of X-ray diffraction) face diffracted intensity < 100, TiN (200) face diffracted intensity >=300.
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