CN103556119B - A kind of preparation method of titanium nitride zirconium niobium nitrogen gradient hard reaction film - Google Patents
A kind of preparation method of titanium nitride zirconium niobium nitrogen gradient hard reaction film Download PDFInfo
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- CN103556119B CN103556119B CN201310514050.7A CN201310514050A CN103556119B CN 103556119 B CN103556119 B CN 103556119B CN 201310514050 A CN201310514050 A CN 201310514050A CN 103556119 B CN103556119 B CN 103556119B
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Abstract
A preparation method for titanium nitride zirconium niobium nitrogen gradient hard reaction film, its preparation method comprises successively: 1, the determination of deposition technique and target material composition; 2, the selection of workpiece and pre-treatment; 3, the determination of pre-bombardment technique; 4, the determination of depositing operation; 5, vacuum heating treatment; 6, workpiece rotates.Present invention reduces coating cost, realize while ensure that low-friction coefficient, high film hardness and high adhesive force, reduce the internal stress of rete, and there is satisfactory stability and repeatability.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen gradient hard reaction film, combination target is particularly adopted to prepare the method for multi-arc ion coating nitrogen gradient hard reaction film, such as the preparation method of titanium nitride zirconium niobium nitrogen gradient hard reaction film (following use " TiZrNbN " replaces " titanium nitride zirconium niobium ").
Background technology
Multi-arc ion coating is a kind of physical vacuum deposition technique being provided with multiple cathodic arc evaporation source that can simultaneously evaporate, have the distinguishing features such as sedimentation velocity is fast, morphology is fine and close, strong adhesion, good uniformity, this technology is applicable to the preparation of hard films and hard reaction gradient film.Initial TiAlN thin film, has higher hardness and is widely used.In order to improve the over-all properties of TiN further, develop binary alloy nitride film, such as, the titanium based hard reaction films such as titanium nitride zirconium, titanium niobium nitride, TiAlN have more development prospect due to respective characteristics such as hardness are high, frictional coefficient is little, thermotolerance is strong than titanium nitride film, meanwhile, the trend of the diversification of hard film layer forward, multiple stratification, Composite is fast-developing.
For individual layer with titanium be base multicomponent hard reaction film for, mainly there is following shortcoming: 1, the general easy contradiction occurred between film hardness and film adhesion, namely hardness and sticking power are difficult to meet simultaneously; 2, multicomponent alloy target market is not easily bought, usually need special melting, processing, not only cost is higher, and the cycle is longer; 3, easily there are " macrobead " (be also referred to as " drop ", size is at 5 ~ 10 microns) in multi-arc ion coating hard reaction film film surface, and more " macrobead " affects the frictional behaviour of rete; 4, in rete, produce larger internal stress, affect result of use and the work-ing life of hard films.
Summary of the invention
The object of this invention is to provide a kind of preparation method of titanium nitride zirconium niobium (TiZrNbN) nitrogen gradient hard reaction film, this method reduce coating cost, realize while ensure that low-friction coefficient, high film hardness and high adhesive force, reduce the internal stress of rete, and there is satisfactory stability and repeatability.
Technical scheme of the present invention is: a kind of preparation method of titanium nitride zirconium niobium (TiZrNbN) nitrogen gradient hard reaction film comprises successively:
1, the determination of deposition technique and target material composition: determine the technology of preparing of multi-arc ion coating as TiZrNbN nitrogen gradient hard reaction film, select two different azimuth and become the arc source starting the arc simultaneously of 90 degree of configurations to deposit, one of them arc source is the commercial titanium-niobium alloy target of purity 99.9%, and the atomic ratio of titanium-niobium alloy target is Ti:Nb=75:25; Another arc source is the commercial zirconium simple substance target of purity 99.9%.
2, the selection of workpiece and pre-treatment: select commercial rapid steel as workpiece material, before putting into coating chamber and carrying out plated film, use to workpiece, metal detergent carries out that routine is deoiled, decontamination process carry out surface finish process, finally carry out ultrasonic cleaning with acetone and ethanol respectively, hair dryer dries up with for subsequent use.
3, the determination of pre-bombardment technique: refer to the ion bombardment technique of carrying out before the deposition for obtaining multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film, when coating chamber back end vacuum reaches 8.0 ' 10
-3handkerchief, temperature are filled with argon gas when reaching 200 ° of C, make coating chamber vacuum tightness reach 2.5 ' 10
-1handkerchief, opens two arc sources, keeps arc current at 55 ~ 56 amperes, carries out ion bombardment 10 ~ 12 minutes, and bombardment bias voltage is increased to 350 volts gradually from 300 volts.
4, the determination of depositing operation: refer to the depositing operation adopted for obtaining multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film, coating process is divided into four-stage, the first step, and the ar pressure in coating chamber is remained on 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 ~ 56 amperes, and workpiece bias is 200 volts, depositing time 5 minutes; Second step, passes into nitrogen in coating chamber, makes its partial pressure reach 1.0 ' 10
-1handkerchief, then adjusts argon flow amount, makes mixed gas total pressure remain on 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 ~ 56 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 10 minutes; 3rd step, close Ar inlet, make argon flow amount be 0, partial pressure of ar gas is 0, and continues to increase nitrogen flow, makes its pressure reach 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 ~ 56 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 20 minutes; 4th step, makes nitrogen pressure reach 3.0 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 ~ 56 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 20 minutes.
5, vacuum heating treatment: comprise workpiece heat and rete baking, workpiece heat mode adopts electric heating element Baking out, reaches 3.0 ' 10 in coating chamber back end vacuum
-2start workpiece heat during handkerchief, heat-up rate remains on 3 ~ 5 ° of C/ minute, can reach 200 ° of C after one hour; Rete baking refers to that deposition process terminates to carry out post-heating baking to deposited TiZrNbN nitrogen gradient hard reaction film afterwards, and adopt small area analysis to carry out micro-heating 10 ~ 15 minutes, electric current is reduced to 50 amperes from 70 amperes gradually.
6, workpiece rotates: in the whole process of workpiece heat, ion bombardment, film deposition, rete baking, holding workpiece rotates always, and rotating speed is 4 ~ 6 revs/min.
The method of multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film is prepared according to employing titanium-niobium alloy target proposed by the invention and zirconium simple substance target combination target, above-mentioned TiZrNbN nitrogen gradient hard reaction film can be obtained, the nitrogen content distribution gradient of this TiZrNbN nitrogen gradient hard reaction film, strong adhesion (3200N), hardness high (3HV3300), film surface " drop " quantity is few, frictional coefficient low (in the wearing and tearing of ball disc type, under material is the test condition of silicon carbide ceramics ball to mill, frictional coefficient is between 0.1 ~ 0.3).
Compared with the existing technology, the present invention determines the technology of preparing of conventional general multi-arc ion coating as TiZrNbN nitrogen gradient hard reaction film, determine commercial titanium-niobium alloy target and zirconium simple substance target as arc source, avoid special smelting, prepare the limitation of titanium zirconium-niobium alloy target, reduce coating cost, the present invention determines target material composition, quantity and configuration orientation, determine commercial rapid steel as workpiece material, determine workpiece pre-treating technology and depositing operation, ensure that prepared TiZrNbN nitrogen gradient hard reaction film has obvious nitrogen content Gradient distribution on coating growth direction, ensure that the quantity of film surface " drop " reduces, size reduces, and then ensure that high film hardness, realize while high adhesive force and low-friction coefficient and there is satisfactory stability and repeatability, advantageously the friction durability of improving TiZrNbN nitrogen gradient hard reaction film, be more suitable for the application at Tool Industry.
Embodiment
embodiment 1
At commercial rapid steel (W18Cr4V) upper preparation TiZrNbN nitrogen gradient hard reaction film, its method is:
1, the determination of deposition technique and target material composition: determine the technology of preparing of multi-arc ion coating as TiZrNbN nitrogen gradient hard reaction film, select two different azimuth and become the arc source starting the arc simultaneously of 90 degree of configurations to deposit, one of them arc source is the commercial titanium-niobium alloy target of purity 99.9%, and the atomic ratio of titanium-niobium alloy target is Ti:Nb=75:25; Another arc source is the commercial zirconium simple substance target of purity 99.9%.
2, the selection of workpiece and pre-treatment: select commercial rapid steel (W18Cr4V) as workpiece material, before putting into coating chamber and carrying out plated film, use to workpiece, metal detergent carries out that routine is deoiled, decontamination process carry out surface finish process, finally carry out ultrasonic cleaning with acetone and ethanol respectively, hair dryer dries up with for subsequent use.
3, the determination of pre-bombardment technique: refer to the ion bombardment technique of carrying out before the deposition for obtaining multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film, when coating chamber back end vacuum reaches 8.0 ' 10
-3handkerchief, temperature are filled with argon gas when reaching 200 ° of C, make coating chamber vacuum tightness reach 2.5 ' 10
-1handkerchief, opens two arc sources, keeps arc current at 55 amperes, carries out ion bombardment 12 minutes, and bombardment bias voltage is increased to 350 volts gradually from 300 volts.
4, the determination of depositing operation: refer to the depositing operation adopted for obtaining multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film, coating process is divided into four-stage, the first step, and the ar pressure in coating chamber is remained on 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 56 amperes, and workpiece bias is 200 volts, depositing time 5 minutes; Second step, passes into nitrogen in coating chamber, makes its partial pressure reach 1.0 ' 10
-1handkerchief, then adjusts argon flow amount, makes mixed gas total pressure remain on 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 56 amperes, and workpiece bias is 200 volts, depositing time 10 minutes; 3rd step, close Ar inlet, make argon flow amount be 0, partial pressure of ar gas is 0, and continues to increase nitrogen flow, makes its pressure reach 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 56 amperes, and workpiece bias is 200 volts, depositing time 20 minutes; 4th step, makes nitrogen pressure reach 3.0 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 56 amperes, and workpiece bias is 200 volts, depositing time 20 minutes.
5, vacuum heating treatment: comprise workpiece heat and rete baking, workpiece heat mode adopts electric heating element Baking out, reaches 3.0 ' 10 in coating chamber back end vacuum
-2start workpiece heat during handkerchief, heat-up rate remains on 3 ~ 5 ° of C/ minute, reaches 200 ° of C after one hour; Rete baking refers to that deposition process terminates to carry out post-heating baking to deposited TiZrNbN nitrogen gradient hard reaction film afterwards, and adopt small area analysis to carry out micro-heating 15 minutes, electric current is reduced to 50 amperes from 70 amperes gradually.
6, workpiece rotates: in the whole process of workpiece heat, ion bombardment, film deposition, rete baking, holding workpiece rotates always, and rotating speed is 4.5 revs/min.
Test the TiZrNbN nitrogen gradient hard reaction film using aforesaid method to prepare, the nitrogen content distribution gradient of this TiZrNbN nitrogen gradient hard reaction film, sticking power reaches 200N, and hardness reaches HV3350, and frictional coefficient is between 0.15 ~ 0.3.
embodiment 2
At commercial rapid steel (W18Cr4V) upper preparation TiZrNbN nitrogen gradient hard reaction film, its method is:
1, the determination of deposition technique and target material composition: determine the technology of preparing of multi-arc ion coating as TiZrNbN nitrogen gradient hard reaction film, select two different azimuth and become the arc source starting the arc simultaneously of 90 degree of configurations to deposit, one of them arc source is the commercial titanium-niobium alloy target of purity 99.9%, and the atomic ratio of titanium-niobium alloy target is Ti:Nb=75:25; Another arc source is the commercial zirconium simple substance target of purity 99.9%.
2, the selection of workpiece and pre-treatment: select commercial rapid steel (W18Cr4V) as workpiece material, before putting into coating chamber and carrying out plated film, use to workpiece, metal detergent carries out that routine is deoiled, decontamination process carry out surface finish process, finally carry out ultrasonic cleaning with acetone and ethanol respectively, hair dryer dries up with for subsequent use.
3, the determination of pre-bombardment technique: refer to the ion bombardment technique of carrying out before the deposition for obtaining multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film, when coating chamber back end vacuum reaches 8.0 ' 10
-3handkerchief, temperature are filled with argon gas when reaching 200 ° of C, make coating chamber vacuum tightness reach 2.5 ' 10
-1handkerchief, opens two arc sources, keeps arc current at 56 amperes, carries out ion bombardment 10 minutes, and bombardment bias voltage is increased to 350 volts gradually from 300 volts.
4, the determination of depositing operation: refer to the depositing operation adopted for obtaining multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film, coating process is divided into four-stage, the first step, and the ar pressure in coating chamber is remained on 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 amperes, and workpiece bias is 200 volts, depositing time 5 minutes; Second step, passes into nitrogen in coating chamber, makes its partial pressure reach 1.0 ' 10
-1handkerchief, then adjusts argon flow amount, makes mixed gas total pressure remain on 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 amperes, and workpiece bias is 150 volts, depositing time 10 minutes; 3rd step, close Ar inlet, make argon flow amount be 0, partial pressure of ar gas is 0, and continues to increase nitrogen flow, makes its pressure reach 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 amperes, and workpiece bias is 150 volts, depositing time 20 minutes; 4th step, makes nitrogen pressure reach 3.0 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 amperes, and workpiece bias is 150 volts, depositing time 20 minutes.
5, vacuum heating treatment: comprise workpiece heat and rete baking, workpiece heat mode adopts electric heating element Baking out, reaches 3.0 ' 10 in coating chamber back end vacuum
-2start workpiece heat during handkerchief, heat-up rate remains on 3 ~ 5 ° of C/ minute, reaches 200 ° of C after one hour; Rete baking refers to that deposition process terminates to carry out post-heating baking to deposited TiZrNbN nitrogen gradient hard reaction film afterwards, and adopt small area analysis to carry out micro-heating 10 minutes, electric current is reduced to 50 amperes from 70 amperes gradually.
6, workpiece rotates: in the whole process of workpiece heat, ion bombardment, film deposition, rete baking, holding workpiece rotates always, and rotating speed is 5.5 revs/min.
Test the TiZrNbN nitrogen gradient hard reaction film using aforesaid method to prepare, the nitrogen content distribution gradient of this TiZrNbN nitrogen gradient hard reaction film, sticking power reaches more than 200N, and hardness reaches HV3400, and frictional coefficient is between 0.1 ~ 0.25.
Claims (1)
1. the preparation method of a titanium nitride zirconium niobium nitrogen gradient hard reaction film, it is characterized in that: its preparation method comprises successively: the determination of (1), deposition technique and target material composition: determine the technology of preparing of multi-arc ion coating as TiZrNbN nitrogen gradient hard reaction film, select two different azimuth and become the arc source starting the arc simultaneously of 90 degree of configurations to deposit, one of them arc source is the commercial titanium-niobium alloy target of purity 99.9%, and the atomic ratio of titanium-niobium alloy target is Ti:Nb=75:25; Another arc source is the commercial zirconium simple substance target of purity 99.9%; (2), the selection of workpiece and pre-treatment: select commercial rapid steel as workpiece material, before putting into coating chamber and carrying out plated film, use to workpiece, metal detergent carries out that routine is deoiled, decontamination process carry out surface finish process, finally carry out ultrasonic cleaning with acetone and ethanol respectively, hair dryer dries up with for subsequent use; (3), the determination of pre-bombardment technique: refer to the ion bombardment technique of carrying out before the deposition for obtaining multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film, when coating chamber back end vacuum reaches 8.0 ' 10
-3handkerchief, temperature are filled with argon gas when reaching 200 ° of C, make coating chamber vacuum tightness reach 2.5 ' 10
-1handkerchief, opens two arc sources, keeps arc current at 55 ~ 56 amperes, carries out ion bombardment 10 ~ 12 minutes, and bombardment bias voltage is increased to 350 volts gradually from 300 volts; (4), the determination of depositing operation: refer to the depositing operation adopted for obtaining multi-arc ion coating TiZrNbN nitrogen gradient hard reaction film, coating process is divided into four-stage, the first step, and the ar pressure in coating chamber is remained on 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 ~ 56 amperes, and workpiece bias is 200 volts, depositing time 5 minutes; Second step, passes into nitrogen in coating chamber, makes its partial pressure reach 1.0 ' 10
-1handkerchief, then adjusts argon flow amount, makes mixed gas total pressure remain on 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 ~ 56 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 10 minutes; 3rd step, close Ar inlet, make argon flow amount be 0, partial pressure of ar gas is 0, and continues to increase nitrogen flow, makes its pressure reach 2.5 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 ~ 56 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 20 minutes; 4th step, makes nitrogen pressure reach 3.0 ' 10
-1handkerchief, the arc current of zirconium simple substance target and titanium-niobium alloy target is all placed in 55 ~ 56 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 20 minutes; (5), vacuum heating treatment: comprise workpiece heat and rete baking, workpiece heat mode adopts electric heating element Baking out, reaches 3.0 ' 10 in coating chamber back end vacuum
-2start workpiece heat during handkerchief, heat-up rate remains on 3 ~ 5 ° of C/ minute, can reach 200 ° of C after one hour; Rete baking refers to that deposition process terminates to carry out post-heating baking to deposited TiZrNbN nitrogen gradient hard reaction film afterwards, and adopt small area analysis to carry out micro-heating 10 ~ 15 minutes, electric current is reduced to 50 amperes from 70 amperes gradually; (6), workpiece rotates: in the whole process of workpiece heat, ion bombardment, film deposition, rete baking, holding workpiece rotates always, and rotating speed is 4 ~ 6 revs/min.
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| CN104911539A (en) * | 2015-06-03 | 2015-09-16 | 陕西航天导航设备有限公司 | Method for preparing titanium nitride film |
| CN104911550A (en) * | 2015-06-03 | 2015-09-16 | 陕西航天导航设备有限公司 | Method for preparing titanium nitride film |
| CN107794504A (en) * | 2017-11-07 | 2018-03-13 | 东南大学 | TiZrTaN coated cutting tools and preparation method thereof |
| CN112281116B (en) * | 2020-09-24 | 2023-01-17 | 北京北方华创微电子装备有限公司 | Thin film electrode manufacturing method, thin film electrode and memory |
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| EP2072636B1 (en) * | 2007-12-21 | 2016-08-31 | Sandvik Intellectual Property AB | Method of making a coated cutting tool |
| US8021768B2 (en) * | 2009-04-07 | 2011-09-20 | National Material, L.P. | Plain copper foodware and metal articles with durable and tarnish free multiplayer ceramic coating and method of making |
| CN101709450B (en) * | 2009-11-30 | 2011-06-15 | 沈阳大学 | Method for preparing zirconium-titanium-aluminum-nitrogen nitride gradient hard reaction film |
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