CN103572219A - Method for preparing nitrogen-gradient hard reaction membrane of chromium titanium niobium nitride (CrTiNbN) - Google Patents
Method for preparing nitrogen-gradient hard reaction membrane of chromium titanium niobium nitride (CrTiNbN) Download PDFInfo
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Abstract
The invention relates to a method for preparing a nitrogen-gradient hard reaction membrane of chromium titanium niobium nitride (CrTiNbN). The method sequentially comprises the following steps of 1. confirmation of a deposition technique and ingredients of target materials; 2. selection and pretreatment of workpieces; 3. confirmation of a preliminary bombardment process; 4. confirmation of a deposition process; 5. vacuum heating treatment; 6. workpiece revolution. According to the method, the cost for coating is lowered, low friction coefficient, high membrane hardness and high adhesive force are guaranteed, furthermore, the inner stress of the membrane is reduced, and the reaction membrane has good stability and repeatability.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen gradient hard reaction film, particularly adopt combination target to prepare the method for multi-arc ion coating nitrogen gradient hard reaction film, such as the chromium nitride titanium niobium nitrogen gradient hard reaction film preparation method of (following use " CrTiNbN " replaces " chromium nitride titanium niobium ").
Background technology
Multi-arc ion coating is a kind of physical vacuum deposition technique that is provided with a plurality of cathodic arc evaporation sources 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.From rete, develop, TiAlN, chromium nitride, the hard composite membranes such as titanium niobium nitride are due to the characteristic and have more development and application values than titanium nitride film separately such as hardness is high, frictional coefficient is little, thermotolerance is strong, and to more diversification, multiple stratification, the Composite Development of high-performance.
For take for the multicomponent hard reaction film that titanium is base of individual layer, mainly there is following shortcoming: 1, the general easy contradiction occurring between film hardness and film adhesion, hardness and sticking power are difficult to meet simultaneously; 2, on multicomponent alloy target market, be difficult for buying, 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 preparation method who the object of this invention is to provide a kind of chromium nitride titanium niobium (CrTiNbN) nitrogen gradient hard reaction film, the method has reduced coating cost, when having guaranteed low-friction coefficient, high film hardness and high adhesive force, realize, reduce the internal stress of rete, and there is satisfactory stability and repeatability.
Technical scheme of the present invention is: the preparation method of a kind of chromium nitride titanium niobium (CrTiNbN) nitrogen gradient hard reaction film comprises successively:
1, determining of deposition technique and target composition: determine that multi-arc ion coating is as the technology of preparing of CrTiNbN nitrogen gradient hard reaction film, select two different azimuth and become the arc source starting the arc simultaneously of 90 degree 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 chromium simple substance target of purity 99.9%.
2, the selection of workpiece and pre-treatment: select commercial rapid steel as workpiece material, carry out before plated film putting into coating chamber, use metal detergent workpiece to be carried out to routine is deoiled, decontamination is processed and carry out surface finish processing, finally with acetone and ethanol, carry out ultrasonic cleaning respectively, hair dryer dries up with standby.
3, bombard in advance determining of technique: refer to the ion bombardment technique of carrying out for obtaining multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film before deposition, when coating chamber back end vacuum reaches 8.0 ' 10
-3handkerchief, temperature are filled with argon gas while reaching 200 ° of C, make coating chamber vacuum tightness reach 2.5 ' 10
-1handkerchief, opens two arc sources, keeps arc current at 50 ~ 55 amperes, carries out ion bombardment 10 ~ 12 minutes, and bombardment bias voltage is increased to 350 volts gradually from 300 volts.
4, determining of depositing operation: refer to the depositing operation that adopts for obtaining multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film, coating process is divided into four-stage, and the first step remains on 2.5 ' 10 by the ar pressure in coating chamber
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 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, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 10 minutes; The 3rd step, closes argon gas entrance, and making argon flow amount is 0, and partial pressure of ar gas is 0, and continues to increase nitrogen flow, makes its pressure reach 2.5 ' 10
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 20 minutes; The 4th step, makes nitrogen pressure reach 3.0 ' 10
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 20 minutes.
5, vacuum heating treatment: comprise workpiece heating and rete baking, workpiece type of heating employing electric heating element Baking out, when workpiece heats, heat-up rate remain on 3 ~ 5 ° of C/minute, after one hour, can reach 200 ° of C; Rete baking refers to that deposition process finishes the rear post-heating baking that deposited CrTiNbN nitrogen gradient hard reaction film is carried out, and adopts little electric current to carry out micro-heating 10 ~ 12 minutes, and electric current is reduced to 30 amperes from 60 amperes gradually.
6, workpiece rotation: holding workpiece rotation always in the whole process of workpiece heating, ion bombardment, film deposition, rete baking, rotating speed is 4 ~ 6 revs/min.
The method of preparing multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film according to employing titanium niobium alloy target proposed by the invention and chromium simple substance target combination target, can obtain above-mentioned CrTiNbN nitrogen gradient hard reaction film, the nitrogen content distribution gradient of this CrTiNbN nitrogen gradient hard reaction film, strong adhesion (3200N), hardness high (3HV3300), film surface " drop " quantity is few, frictional coefficient low (being that under the test condition of silicon carbide ceramics ball, frictional coefficient is between 0.15 ~ 0.4 in the wearing and tearing of ball disc type, to mill material).
Compared with the existing technology, the present invention has determined that conventional general multi-arc ion coating is as the technology of preparing of CrTiNbN nitrogen gradient hard reaction film, determined that commercial titanium niobium alloy target and chromium simple substance target are as arc source, avoid special smelting, prepared the limitation of chromium titanium niobium alloy target, reduced coating cost, the present invention has determined target composition, quantity and configuration orientation, determined that commercial rapid steel is as workpiece material, workpiece pre-treating technology and depositing operation have been determined, guaranteed that prepared CrTiNbN nitrogen gradient hard reaction film has obvious nitrogen content Gradient distribution in coating growth direction, the quantity that has guaranteed film surface " drop " reduces, size reduction, and then guaranteed high film hardness, in the time of high adhesive force and low-friction coefficient, realize and there is satisfactory stability and repeatability, more be conducive to improve the friction durability of CrTiNbN nitrogen gradient hard reaction film, be more suitable in the application at Tool Industry.
Embodiment
embodiment 1
At the upper preparation of commercial rapid steel (W18Cr4V) CrTiNbN nitrogen gradient hard reaction film, its method is:
1, determining of deposition technique and target composition: determine that multi-arc ion coating is as the technology of preparing of CrTiNbN nitrogen gradient hard reaction film, select two different azimuth and become the arc source starting the arc simultaneously of 90 degree 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 chromium simple substance target of purity 99.9%.
2, the selection of workpiece and pre-treatment: select commercial rapid steel (W18Cr4V) as workpiece material, carry out before plated film putting into coating chamber, use metal detergent workpiece to be carried out to routine is deoiled, decontamination is processed and carry out surface finish processing, finally with acetone and ethanol, carry out ultrasonic cleaning respectively, hair dryer dries up with standby.
3, bombard in advance determining of technique: refer to the ion bombardment technique of carrying out for obtaining multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film before deposition, when coating chamber back end vacuum reaches 8.0 ' 10
-3handkerchief, temperature are filled with argon gas while reaching 200 ° of C, make coating chamber vacuum tightness reach 2.5 ' 10
-1handkerchief, opens two arc sources, keeps arc current at 52 amperes, carries out ion bombardment 10 minutes, and bombardment bias voltage is increased to 350 volts gradually from 300 volts.
4, determining of depositing operation: refer to the depositing operation that adopts for obtaining multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film, coating process is divided into four-stage, and the first step remains on 2.5 ' 10 by the ar pressure in coating chamber
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 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, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 200 volts, depositing time 10 minutes; The 3rd step, closes argon gas entrance, and making argon flow amount is 0, and partial pressure of ar gas is 0, and continues to increase nitrogen flow, makes its pressure reach 2.5 ' 10
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 200 volts, depositing time 20 minutes; The 4th step, makes nitrogen pressure reach 3.0 ' 10
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 200 volts, depositing time 20 minutes.
5, vacuum heating treatment: comprise workpiece heating and rete baking, workpiece type of heating employing electric heating element Baking out, when workpiece heats, heat-up rate remain on 3 ~ 5 ° of C/minute, after one hour, reach 200 ° of C; Rete baking refers to that deposition process finishes the rear post-heating baking that deposited CrTiNbN nitrogen gradient hard reaction film is carried out, and adopts little electric current to carry out micro-heating 10 minutes, and electric current is reduced to 30 amperes from 60 amperes gradually.
6, workpiece rotation: holding workpiece rotation always in the whole process of workpiece heating, ion bombardment, film deposition, rete baking, rotating speed is 5 revs/min.
The CrTiNbN nitrogen gradient hard reaction film that uses aforesaid method to prepare is tested, the nitrogen content distribution gradient of this CrTiNbN nitrogen gradient hard reaction film, strong adhesion (>200N), hardness high (HV3380), frictional coefficient low (0.2 ~ 0.35).
embodiment 2
At the upper preparation of commercial rapid steel (W18Cr4V) CrTiNbN nitrogen gradient hard reaction film, its method is:
1, determining of deposition technique and target composition: determine that multi-arc ion coating is as the technology of preparing of CrTiNbN nitrogen gradient hard reaction film, select two different azimuth and become the arc source starting the arc simultaneously of 90 degree 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 chromium simple substance target of purity 99.9%.
2, the selection of workpiece and pre-treatment: select commercial rapid steel (W18Cr4V) as workpiece material, carry out before plated film putting into coating chamber, use metal detergent workpiece to be carried out to routine is deoiled, decontamination is processed and carry out surface finish processing, finally with acetone and ethanol, carry out ultrasonic cleaning respectively, hair dryer dries up with standby.
3, bombard in advance determining of technique: refer to the ion bombardment technique of carrying out for obtaining multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film before deposition, when coating chamber back end vacuum reaches 8.0 ' 10
-3handkerchief, temperature are filled with argon gas while reaching 200 ° of C, make coating chamber vacuum tightness reach 2.5 ' 10
-1handkerchief, opens two arc sources, keeps arc current at 54 amperes, carries out ion bombardment 12 minutes, and bombardment bias voltage is increased to 350 volts gradually from 300 volts.
4, determining of depositing operation: refer to the depositing operation that adopts for obtaining multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film, coating process is divided into four-stage, and the first step remains on 2.5 ' 10 by the ar pressure in coating chamber
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 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, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 volts, depositing time 10 minutes; The 3rd step, closes argon gas entrance, and making argon flow amount is 0, and partial pressure of ar gas is 0, and continues to increase nitrogen flow, makes its pressure reach 2.5 ' 10
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 volts, depositing time 20 minutes; The 4th step, makes nitrogen pressure reach 3.0 ' 10
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 volts, depositing time 20 minutes.
5, vacuum heating treatment: comprise workpiece heating and rete baking, workpiece type of heating employing electric heating element Baking out, when workpiece heats, heat-up rate remain on 3 ~ 5 ° of C/minute, after one hour, reach 200 ° of C; Rete baking refers to that deposition process finishes the rear post-heating baking that deposited CrTiNbN nitrogen gradient hard reaction film is carried out, and adopts little electric current to carry out micro-heating 10 minutes, and electric current is reduced to 30 amperes from 60 amperes gradually.
6, workpiece rotation: holding workpiece rotation always in the whole process of workpiece heating, ion bombardment, film deposition, rete baking, rotating speed is 5 revs/min.
The CrTiNbN nitrogen gradient hard reaction film that uses aforesaid method to prepare is tested, the nitrogen content distribution gradient of this CrTiNbN nitrogen gradient hard reaction film, strong adhesion (>200N), hardness high (HV3420), frictional coefficient low (0.15 ~ 0.3).
Claims (1)
1. the preparation method of a chromium nitride titanium niobium nitrogen gradient hard reaction film, it is characterized in that: its preparation method comprises successively: the determining of (1), deposition technique and target composition: determine that multi-arc ion coating is as the technology of preparing of CrTiNbN nitrogen gradient hard reaction film, select two different azimuth and become the arc source starting the arc simultaneously of 90 degree 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 chromium simple substance target of purity 99.9%; (2), the selection of workpiece and pre-treatment: select commercial rapid steel as workpiece material, carry out before plated film putting into coating chamber, use metal detergent workpiece to be carried out to routine is deoiled, decontamination is processed and carry out surface finish processing, finally with acetone and ethanol, carry out ultrasonic cleaning respectively, hair dryer dries up with standby; (3) bombard, in advance determining of technique: refer to the ion bombardment technique of carrying out for obtaining multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film before deposition, when coating chamber back end vacuum reaches 8.0 ' 10
-3handkerchief, temperature are filled with argon gas while reaching 200 ° of C, make coating chamber vacuum tightness reach 2.5 ' 10
-1handkerchief, opens two arc sources, keeps arc current at 50 ~ 55 amperes, carries out ion bombardment 10 ~ 12 minutes, and bombardment bias voltage is increased to 350 volts gradually from 300 volts; (4), the determining of depositing operation: refer to the depositing operation that adopts for obtaining multi-arc ion coating CrTiNbN nitrogen gradient hard reaction film, coating process is divided into four-stage, and the first step remains on 2.5 ' 10 by the ar pressure in coating chamber
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 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, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 10 minutes; The 3rd step, closes argon gas entrance, and making argon flow amount is 0, and partial pressure of ar gas is 0, and continues to increase nitrogen flow, makes its pressure reach 2.5 ' 10
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 20 minutes; The 4th step, makes nitrogen pressure reach 3.0 ' 10
-1handkerchief, chromium simple substance target arc current is 50 amperes, and the arc current of titanium niobium alloy target is 55 amperes, and workpiece bias is 150 ~ 200 volts, depositing time 20 minutes; (5), vacuum heating treatment: comprise workpiece heating and rete baking, workpiece type of heating employing electric heating element Baking out, when workpiece heats, heat-up rate remain on 3 ~ 5 ° of C/minute, after one hour, can reach 200 ° of C; Rete baking refers to that deposition process finishes the rear post-heating baking that deposited CrTiNbN nitrogen gradient hard reaction film is carried out, and adopts little electric current to carry out micro-heating 10 ~ 12 minutes, and electric current is reduced to 30 amperes from 60 amperes gradually; (6), workpiece rotation: holding workpiece rotation always in the whole process of workpiece heating, ion bombardment, film deposition, rete baking, rotating speed is 4 ~ 6 revs/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726824A (en) * | 2015-04-14 | 2015-06-24 | 沈阳大学 | Titanium nitride-aluminium-zirconium/titanium nitride-aluminium-zirconium-silicon quaternary double layer nitride film preparation method |
| CN112281116A (en) * | 2020-09-24 | 2021-01-29 | 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 |
| CN114150261A (en) * | 2021-11-30 | 2022-03-08 | 昆山英利悦电子有限公司 | Chromium nitride coating process for automobile sound panel |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104726824A (en) * | 2015-04-14 | 2015-06-24 | 沈阳大学 | Titanium nitride-aluminium-zirconium/titanium nitride-aluminium-zirconium-silicon quaternary double layer nitride film preparation method |
| CN112281116A (en) * | 2020-09-24 | 2021-01-29 | 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 |
| CN114150261A (en) * | 2021-11-30 | 2022-03-08 | 昆山英利悦电子有限公司 | Chromium nitride coating process for automobile sound panel |
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