CN106048525A - Preparation method of titanium-chromium metal nitride composite hard film with continuous change - Google Patents

Preparation method of titanium-chromium metal nitride composite hard film with continuous change Download PDF

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Publication number
CN106048525A
CN106048525A CN201610555564.0A CN201610555564A CN106048525A CN 106048525 A CN106048525 A CN 106048525A CN 201610555564 A CN201610555564 A CN 201610555564A CN 106048525 A CN106048525 A CN 106048525A
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arc
deposition
film
titanium
handkerchief
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CN106048525B (en
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张钧
戴步实
赵微
王宇
张正贵
刘世民
丁龙先
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Jilin effort Technology Co., Ltd.
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Shenyang University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties

Abstract

The invention discloses a preparation method of a titanium-chromium metal nitride composite hard film with continuous change, and relates to a preparation method of a metal film. The method comprises the following steps of determining a deposition technique, determining an arc source target material, determining the number of arc sources, selecting and preprocessing a to-be-coated metal substrate, determining a pre-baking process, determining a pre-bombarding cleaning process, determining a preparation process of a titanium-chromium alloy transition layer, determining deposition time, controlling reaction gas partial pressure corresponding to the deposition time, determining arc source target arc current corresponding to the deposition time, determining substrate negative bias voltage corresponding to the deposition time, controlling the temperature of a coating chamber, and performing rotary coating on a workpiece frame. By using the method, the quasi-linear continuous change of film components from the metal substrate to the surface of the film is guaranteed, and the internal stress of a component difference interface in the film due to large component change is reduced, so that high adhesion, high hardness and high thermal shock property are simultaneously achieved, and good stability is obtained.

Description

A kind of preparation method of continually varying titanium chromium metal nitride composite ganoine film
Technical field
The present invention relates to the preparation method of a kind of metal film, become continuously especially with multi sphere ion plating technology prepared composition The method of the metal nitride composite ganoine film changed, the such as preparation side of continually varying titanium chromium metal nitride composite ganoine film Method.
Background technology
Multi-arc ion coating is a kind of physical gas phase deposition technology being provided with multiple cathodic arc evaporation source that can simultaneously evaporate, tool There are the distinguishing features such as deposition velocity is fast, morphology is fine and close, adhesive force is strong, uniformity is good.It is anti-that this technology is applicable to various hard Answer the preparation of film, and the application that succeeds in terms of the preparation of nitride hard reaction film.
For the nitride hard reaction film with titanium as base of monolayer, bilayer and gradient components change, generally there are Following shortcoming: 1, in morphology, easy appearance significantly has the interface of composition difference, causes the discontinuous change of membranous layer ingredient Change；2, easily occur that the contradiction between film hardness and film adhesion, i.e. hardness and adhesive force are difficult to meet simultaneously；3, easy In film layer, produce bigger internal stress, affect the thermal shock performance of hard reaction film, and then affect using effect and service life.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of continually varying titanium chromium metal nitride composite ganoine film, should Method ensure that membranous layer ingredient almost linear consecutive variations from metallic matrix to film surface, reduces Mo Cengzhong component difference circle The internal stress that face causes owing to composition transfer is relatively big, thus real while ensure that high adhesion force, high rigidity and highly heatproof and shockproof Existing, and there is good stability.
The technical scheme is that
The preparation method of a kind of continually varying titanium chromium metal nitride composite ganoine film includes successively:
1, the determination of deposition technique: determine the multi-arc ion coating system as composition continually varying titanium chromium nitride composite ganoine film Standby technology.
2, the determination of arc source target: determine purity be 99.99% titanium target and chromium target equal amount combine as plated film arc Source target, or titanium chrome alloy target is as arc source target, the Ti/Cr atomic ratio of titanium chrome alloy target=(55 ~ 50)/(45 ~ 50).
3, the determination of arc source number: require according to membrane uniformity and the temperature limiting of metallic matrix to be coated determines institute Multi-arc ion coating arc source number to be used, i.e. for ensure membrane uniformity, at least select two differing heights different azimuth and Become the starting the arc simultaneously of 90 degree of arc sources of configuring, and to ensure simultaneously metallic matrix to be coated coating chamber whole during, plated film The temperature that room temperature allows less than matrix.
4, the selection of metallic matrix to be coated and pre-treatment: select high-speed steel or hard alloy as Metal Substrate to be coated Body, before putting into coating chamber and carrying out plated film, routine is deoiled, decontamination processes and carries out surface throwing to use metal detergent to carry out it Optical processing, carries out ultrasonic waves for cleaning with acetone and ethanol the most respectively, and hair dryer dries up with standby, is subsequently placed in the work of coating chamber On part frame.
5, the determination of pre-firing processes: refer to as acquisition composition continually varying titanium chromium nitride composite ganoine film at ion Bombardment technique starts the heated baking technique carried out before, reaches 3 × 10 in coating chamber vacuum-2During handkerchief, start baking electricity Stream, for avoiding thermal stress to gather, uses small area analysis to toast, and keeps the work rest uniform rotation of bearing substrate, coating chamber temperature Reaching 200 DEG C of times used is not less than 20 minutes.
6, the determination of pre-Bombardment and cleaning technique: refer to for obtain composition continually varying titanium chromium nitride composite ganoine film and The ion bom bardment technique carried out before plating titanium chrome alloy transition zone, when coating chamber back end vacuum reaches 8.0 × 10-3Handkerchief, pre- Baking temperature reaches to be filled with argon when 200 DEG C, makes coating chamber pressure reach 2.2 × 10-1Handkerchief ~ 2.8 × 10-1Handkerchief, opens each Arc source, according to arc source target size size, keeps stable certain current value between 50 ~ 80 amperes of arc current, carries out ion Bombarding 15 minutes, bombardment bias progressively increases to 400 volts from 350 volts.
7, the determination of the preparation technology of titanium chrome alloy transition zone: the ar pressure in coating chamber is maintained at 2.2 × 10-1 Handkerchief ~ 2.8 × 10-1Handkerchief, the titanium target of equal amount combination and chromium target, or, the arc current of titanium chrome alloy target is placed in 50 ~ 80 peaces Certain current value between training, substrate negative voltage is-200 volts, and arcing time is 10 minutes, and then regulation ar pressure reaches 2.8×10-1Handkerchief, is ready for the deposition of composition continually varying titanium chromium nitride composite ganoine film.
8, the determination of sedimentation time: refer to that determine for obtaining composition continually varying titanium chromium nitride composite ganoine film sinks The long-pending time, the number according to the multi-arc ion coating arc source used and the thickness requirement to film layer determine whole sedimentation time, so After whole sedimentation time is divided into 3:1, the first half section time wherein deposited is the 3/4 of total sedimentation time, during second half section of deposition Between be the 1/4 of total sedimentation time.
The control of the 9 reacting gas dividing potential drops corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride Composite ganoine film and the reacting gas nitrogen partial pressure that determines controls process, in first half section time of deposition by Flow-rate adjustment, protect Card nitrogen partial pressure uniform speed increase, and reduce partial pressure of ar gas accordingly by Flow-rate adjustment simultaneously so that both in deposition process Total pressure remain 2.8 × 10-1Handkerchief is constant, and at the end of this stage, nitrogen partial pressure reaches 2.8 × 10-1Handkerchief, argon divides Pressure drop is 0 handkerchief, and then keeping nitrogen pressure is 2.8 × 10-1Handkerchief, carries out the deposition of latter half, until deposition terminates.
The determination of the 10 arc source target arc currents corresponding with sedimentation time: refer to as obtaining the nitridation of composition continually varying titanium chromium Thing composite ganoine film and the electric current of arc source target that determines selects, in the first half section time of deposition, keep the arc source target arc used Electric current is consistent with aforesaid method step 6, at the latter half of deposition, adjusts arc source target arc current, the arc of each arc source target Electric current increases by 2 ~ 3 amperes, until deposition process terminates.
The determination of 11 substrate negative voltage corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride Composite ganoine film and the selection of substrate negative voltage that determines, in the first half section time of deposition, substrate negative voltage selects-180 ~- 200 volts, at the latter half of deposition, substrate negative voltage selects at-120 ~-130 volts.
12, the control of coating chamber temperature: refer to determine for obtaining composition continually varying titanium chromium nitride composite ganoine film Coating chamber temperature limiting, for high speed steel substrate, coating chamber temperature not can exceed that 380 degrees Celsius；For hard alloy substrate, Coating chamber temperature not can exceed that 420 degrees Celsius.
13, work rest rotary plating: be slowly heated baking at coating chamber, matrix is carried out ion bom bardment, the conjunction of plating titanium chromium Gold transition zone, composition continually varying titanium chromium nitride composite ganoine film deposition whole during be always maintained at work rest rotation Turning, rotating speed is 6 revs/min.
According to the preparation method of composition continually varying titanium chromium nitride composite ganoine film proposed by the invention, can obtain Obtaining above-mentioned composition continually varying titanium chromium nitride composite ganoine film, this composite ganoine film ensure that membranous layer ingredient is from metal Matrix, to the almost linear consecutive variations of film surface, particularly ensure that N element content standard from metallic matrix to film surface LINEAR CONTINUOUS increases, and is formed without component difference interface, thus ensure that the same of high adhesion force, high rigidity and highly heatproof and shockproof in film layer Shi Shixian, reduces film layer internal stress, and has good stability.
Compared with the existing technology, present invention determine that multi-arc ion coating is combined as composition continually varying titanium chromium nitride The technology of preparing of hard films, it is determined that target material composition, quantity and configuration orientation, it is determined that the selection of metallic matrix to be coated is with front Process technique, pre-Bombardment and cleaning technique, the preparation technology of titanium chrome alloy transition zone, sedimentation time, reacting gas dividing potential drop, arc source target Arc current, substrate negative voltage and coating chamber temperature, it is ensured that membranous layer ingredient almost linear from metallic matrix to film surface is even Continuous change, reduces the internal stress that the component difference interface formed due to composition large change in film layer is caused, thus protects Realize while having demonstrate,proved high adhesion force, high rigidity and highly heatproof and shockproof, and there is good stability, thus advantageously in raising The friction durability of titanium chromium nitride composite ganoine film, it is more suitable for the application at industrial circle.
Detailed description of the invention
Embodiment 1
Prepared composition continually varying titanium chromium nitride composite ganoine film on commercial high speed steel W18Cr4V, its method is:
1, the determination of deposition technique: determine the multi-arc ion coating system as composition continually varying titanium chromium nitride composite ganoine film Standby technology.
2, the determination of arc source target: determine purity be 99.99% titanium target and chromium target equal amount combine as plated film arc Source target.
3, the determination of arc source number: require according to membrane uniformity and the temperature limiting of metallic matrix to be coated determines institute Multi-arc ion coating arc source number to be used, i.e. for ensure membrane uniformity, select 2 titanium targets and 2 chromium targets as arc source, Further, every pair of target, i.e. 1 titanium target and 1 chromium target, is in differing heights different azimuth and becomes 90 degree of configurations, the starting the arc simultaneously, and To ensure simultaneously metallic matrix to be coated coating chamber whole during, coating chamber temperature less than matrix allow temperature.
4, the selection of metallic matrix to be coated and pre-treatment: high speed steel W18Cr4V matrix to be coated enters putting into coating chamber Before row plated film, routine is deoiled, decontamination processes and carries out surface finish process to use metal detergent to carry out it, uses the most respectively Acetone and ethanol carry out ultrasonic waves for cleaning, and hair dryer dries up with standby, is subsequently placed on the work rest of coating chamber.
5, the determination of pre-firing processes: refer to as acquisition composition continually varying titanium chromium nitride composite ganoine film at ion Bombardment technique starts the heated baking technique carried out before, reaches 3 × 10 in coating chamber vacuum-2During handkerchief, start baking electricity Stream, for avoiding thermal stress to gather, uses small area analysis to toast, and keeps the work rest uniform rotation of bearing substrate, coating chamber temperature Reaching 200 DEG C of times used is 23 minutes.
6, the determination of pre-Bombardment and cleaning technique: refer to for obtain composition continually varying titanium chromium nitride composite ganoine film and The ion bom bardment technique carried out before plating titanium chrome alloy transition zone, when coating chamber back end vacuum reaches 8.0 × 10-3Handkerchief, pre- Baking temperature reaches to be filled with argon when 200 DEG C, makes coating chamber pressure reach 2.5 × 10-1Handkerchief, opens each arc source, keeps arc electricity Stream is stable carries out ion bom bardment 15 minutes at 58 amperes, and bombardment bias progressively increases to 400 volts from 350 volts.
7, the determination of the preparation technology of titanium chrome alloy transition zone: the ar pressure in coating chamber is maintained at 2.5 × 10-1 Handkerchief, the arc current of 2 titanium targets and 2 chromium targets is placed in 58 amperes, and substrate negative voltage is-200 volts, and arcing time is 10 minutes, Then regulation ar pressure reaches 2.8 × 10-1Handkerchief, is ready for composition continually varying titanium chromium nitride composite ganoine film Deposition.
8, the determination of sedimentation time: refer to that determine for obtaining composition continually varying titanium chromium nitride composite ganoine film sinks The long-pending time, the number according to the multi-arc ion coating arc source used and the thickness requirement to film layer determine that whole sedimentation time is 80 Minute, then whole sedimentation time being divided into two parts, the first half section time wherein deposited is 60 minutes, during second half section of deposition Between be 20 minutes.
The control of the 9 reacting gas dividing potential drops corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride Composite ganoine film and the reacting gas nitrogen partial pressure that determines controls process, in first half section time of deposition by Flow-rate adjustment, protect Card nitrogen partial pressure uniform speed increase, and reduce partial pressure of ar gas accordingly by Flow-rate adjustment simultaneously so that both in deposition process Total pressure remain 2.8 × 10-1Handkerchief is constant, and at the end of this stage, nitrogen partial pressure reaches 2.8 × 10-1Handkerchief, argon divides Pressure drop is 0 handkerchief, and then keeping nitrogen pressure is 2.8 × 10-1Handkerchief, carries out the deposition of latter half, until deposition terminates.
The determination of the 10 arc source target currents corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride Composite ganoine film and the electric current of arc source target that determines selects, in the first half section time of deposition, keep the arc source target arc electricity used Flowing consistent with aforesaid method step 6, the arc current of each arc source target is stable at 58 amperes, at the latter half of deposition, adjusts Arc source target arc current, the arc current of each arc source target increases to 60 amperes, until deposition process terminates.
The determination of 11 substrate negative voltage corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride Composite ganoine film and the selection of substrate negative voltage that determines, in the first half section time of deposition, substrate negative voltage selects at-180 volts, At the latter half of deposition, substrate negative voltage selects at-120 volts.
12, the control of coating chamber temperature: refer to determine for obtaining composition continually varying titanium chromium nitride composite ganoine film Coating chamber temperature limiting, in the present embodiment, coating chamber temperature maximum is 310 degrees Celsius.
13, work rest rotary plating: be slowly heated baking at coating chamber, matrix is carried out ion bom bardment, the conjunction of plating titanium chromium Gold transition zone, composition continually varying titanium chromium nitride composite ganoine film deposition whole during be always maintained at work rest rotation Turning, rotating speed is 6 revs/min.
To making the composition continually varying titanium chromium nitride composite ganoine film prepared in aforementioned manners be measured, its film layer Thickness is 2.6 microns, this composite ganoine film membranous layer ingredient almost linear consecutive variations from high speed steel substrate to film surface, film layer Middle N element content almost linear from high speed steel substrate to film surface increases continuously, and does not occur component difference interface in film layer, Realize while ensure that high adhesion force, high rigidity and highly heatproof and shockproof.
Embodiment 2
Prepared composition continually varying titanium chromium nitride composite ganoine film on hard alloy YT15 matrix, its method is:
1, the determination of deposition technique: determine the multi-arc ion coating system as composition continually varying titanium chromium nitride composite ganoine film Standby technology.
2, the determination of arc source target: determine titanium chrome alloy target as arc source target, the Ti/Zr atomic ratio of titanium chrome alloy target= 45.5/54.5。
3, the determination of arc source number: require according to membrane uniformity and the temperature limiting of metallic matrix to be coated determines institute Multi-arc ion coating arc source number to be used, i.e. for ensure membrane uniformity, select 4 titanium chrome alloy targets as arc source, and And, every pair of target is in differing heights different azimuth and becomes 90 degree of configurations, the starting the arc simultaneously, and to ensure metallic matrix to be coated simultaneously Coating chamber whole during, coating chamber temperature less than matrix allow temperature.
4, the selection of metallic matrix to be coated and pre-treatment: hard alloy YT15 matrix to be coated is carried out putting into coating chamber Before plated film, routine is deoiled, decontamination processes and carry out surface finish process, the most respectively with third to use metal detergent to carry out it Ketone and ethanol carry out ultrasonic waves for cleaning, and hair dryer dries up with standby, is subsequently placed on the work rest of coating chamber.
5, the determination of pre-firing processes: refer to as acquisition composition continually varying titanium chromium nitride composite ganoine film at ion Bombardment technique starts the heated baking technique carried out before, reaches 3 × 10 in coating chamber vacuum-2During handkerchief, start baking electricity Stream, for avoiding thermal stress to gather, uses small area analysis to toast, and keeps the work rest uniform rotation of bearing substrate, coating chamber temperature Reaching 200 DEG C of times used is 25 minutes.
6, the determination of pre-Bombardment and cleaning technique: refer to for obtain composition continually varying titanium chromium nitride composite ganoine film and The ion bom bardment technique carried out before plating titanium chrome alloy transition zone, when coating chamber back end vacuum reaches 8.0 × 10-3Handkerchief, pre- Baking temperature reaches to be filled with argon when 200 DEG C, makes coating chamber pressure reach 2.5 × 10-1Handkerchief, opens each arc source, according to arc source Target size size, keeps arc current to stablize at 60 amperes, carries out ion bom bardment 15 minutes, and bombardment bias gradually increases from 350 volts It is added to 400 volts.
7, the determination of the preparation technology of titanium chrome alloy transition zone: the ar pressure in coating chamber is maintained at 2.5 × 10-1 Handkerchief, the arc current of 4 titanium chrome alloy targets is placed in 60 amperes, and substrate negative voltage is-200 volts, and arcing time is 10 minutes, then Regulation ar pressure reaches 2.8 × 10-1Handkerchief, is ready for the deposition of composition continually varying titanium chromium nitride composite ganoine film.
8, the determination of sedimentation time: refer to that determine for obtaining composition continually varying titanium chromium nitride composite ganoine film sinks The long-pending time, the number according to the multi-arc ion coating arc source used and the thickness requirement to film layer determine that whole sedimentation time is 80 Minute, then whole sedimentation time being divided into two parts, the first half section time wherein deposited is 60 minutes, during second half section of deposition Between be 20 minutes.
The control of the 9 reacting gas dividing potential drops corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride Composite ganoine film and the reacting gas nitrogen partial pressure that determines controls process, in first half section time of deposition by Flow-rate adjustment, protect Card nitrogen partial pressure uniform speed increase, and reduce partial pressure of ar gas accordingly by Flow-rate adjustment simultaneously so that both in deposition process Total pressure remain 2.8 × 10-1Handkerchief is constant, and at the end of this stage, nitrogen partial pressure reaches 2.8 × 10-1Handkerchief, argon divides Pressure drop is 0 handkerchief, and then keeping nitrogen pressure is 2.8 × 10-1Handkerchief, carries out the deposition of latter half, until deposition terminates.
The determination of the 10 arc source target currents corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride Composite ganoine film and the electric current of arc source target that determines selects, in the first half section time of deposition, keep the arc source target current used Consistent with aforesaid method step 6, the arc current of each arc source target is stable at 60 amperes, at the latter half of deposition, adjusts arc Source target arc current, the arc current of each arc source target increases to 62 amperes, until deposition process terminates.
The determination of 11 substrate negative voltage corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride Composite ganoine film and the selection of substrate negative voltage that determines, in the first half section time of deposition, substrate negative voltage selects at-200 volts, At the latter half of deposition, substrate negative voltage selects at-130 volts.
12, the control of coating chamber temperature: refer to determine for obtaining composition continually varying titanium chromium nitride composite ganoine film Coating chamber temperature limiting, in the present embodiment, coating chamber temperature maximum is 345 degrees Celsius.
13, work rest rotary plating: be slowly heated baking at coating chamber, matrix is carried out ion bom bardment, the conjunction of plating titanium chromium Gold transition zone, composition continually varying titanium chromium nitride composite ganoine film deposition whole during be always maintained at work rest rotation Turning, rotating speed is 6 revs/min.
To making the composition continually varying titanium chromium nitride composite ganoine film prepared in aforementioned manners be measured, its film layer Thickness is 2.4 microns, this composite ganoine film membranous layer ingredient almost linear consecutive variations from hard alloy substrate to film surface, film In Ceng, N element content almost linear from hard alloy substrate to film surface increases continuously, and does not occur component difference in film layer Interface, it is ensured that realize while high adhesion force, high rigidity and highly heatproof and shockproof.

Claims (1)

1. the preparation method of a continually varying titanium chromium metal nitride composite ganoine film, it is characterised in that described method bag Include procedure below:
1) determination of deposition technique: determine the multi-arc ion coating system as composition continually varying titanium chromium nitride composite ganoine film Standby technology；
2) determination of arc source target: determine purity be 99.99% titanium target and chromium target equal amount combine as plated film arc source Target, or titanium chrome alloy target is as arc source target, the Ti/Cr atomic ratio of titanium chrome alloy target=(55 ~ 50)/(45 ~ 50)；
3) determination of arc source number: require according to membrane uniformity and the temperature limiting of metallic matrix to be coated determines and to make Multi-arc ion coating arc source number, i.e. for ensure membrane uniformity, at least select two differing heights different azimuth and become 90 The arc source simultaneously starting the arc of degree configuration, and to ensure simultaneously metallic matrix to be coated coating chamber whole during, plated film room temperature The temperature that degree allows less than matrix；
4) selection of metallic matrix to be coated and pre-treatment: select high-speed steel or hard alloy as metallic matrix to be coated, Before putting into coating chamber and carrying out plated film, routine is deoiled, decontamination processes and carries out surface finish to use metal detergent to carry out it Processing, carry out ultrasonic waves for cleaning with acetone and ethanol the most respectively, hair dryer dries up with standby, is subsequently placed in the workpiece of coating chamber On frame；
5) determination of pre-firing processes: refer to as acquisition composition continually varying titanium chromium nitride composite ganoine film in ion bom bardment Technique starts the heated baking technique carried out before, reaches 3 × 10 in coating chamber vacuum-2During handkerchief, start baking electric current, for Avoiding thermal stress to gather, use small area analysis to toast, and keep the work rest uniform rotation of bearing substrate, coating chamber temperature reaches 200 DEG C of times used are not less than 20 minutes；
6) determination of pre-Bombardment and cleaning technique: refer to as acquisition composition continually varying titanium chromium nitride composite ganoine film at plating The ion bom bardment technique carried out before titanium chrome alloy transition zone, when coating chamber back end vacuum reaches 8.0 × 10-3Handkerchief, prebake conditions Temperature reaches to be filled with argon when 200 DEG C, makes coating chamber pressure reach 2.2 × 10-1Handkerchief ~ 2.8 × 10-1Handkerchief, opens each arc Source, according to arc source target size size, keeps stable certain current value between 50 ~ 80 amperes of arc current, carries out ion and bang Hitting 15 minutes, bombardment bias progressively increases to 400 volts from 350 volts；
7) determination of the preparation technology of titanium chrome alloy transition zone: the ar pressure in coating chamber is maintained at 2.2 × 10-1Handkerchief ~ 2.8×10-1Handkerchief, equal amount combination titanium target and chromium target, or, the arc current of titanium chrome alloy target be placed in 50 ~ 80 amperes it Between certain current value, substrate negative voltage is-200 volts, and arcing time is 10 minutes, then regulation ar pressure reach 2.8 × 10-1Handkerchief, is ready for the deposition of composition continually varying titanium chromium nitride composite ganoine film；
8) determination of sedimentation time: when referring to the deposition determined for obtaining composition continually varying titanium chromium nitride composite ganoine film Between, the number according to the multi-arc ion coating arc source used and the thickness requirement to film layer determine whole sedimentation time, then will Whole sedimentation time is divided into 3:1, and the first half section time wherein deposited is the 3/4 of total sedimentation time, and the latter half of deposition is The 1/4 of total sedimentation time；
9) control of corresponding with sedimentation time reacting gas dividing potential drop: refer to as obtaining composition continually varying titanium chromium nitride compound Hard films and the reacting gas nitrogen partial pressure that determines controls process, pass through Flow-rate adjustment in the first half section time of deposition, it is ensured that nitrogen Edema caused by disorder of QI pressure uniform speed increase, and reduce partial pressure of ar gas accordingly by Flow-rate adjustment simultaneously so that in deposition process, the two is total Pressure remains 2.8 × 10-1Handkerchief is constant, and at the end of this stage, nitrogen partial pressure reaches 2.8 × 10-1Handkerchief, partial pressure of ar gas drops Being 0 handkerchief, then keeping nitrogen pressure is 2.8 × 10-1Handkerchief, carries out the deposition of latter half, until deposition terminates；
10) determination of corresponding with sedimentation time arc source target arc current: refer to as obtaining composition continually varying titanium chromium nitride multiple The electric current of the arc source target closing hard films and determine selects, and in the first half section time of deposition, keeps the arc source target arc current used Consistent with aforesaid method step 6, at the latter half of deposition, adjust arc source target arc current, the arc current of each arc source target Increase by 2 ~ 3 amperes, until deposition process terminates；
11) determination of the substrate negative voltage corresponding with sedimentation time: refer to as obtaining composition continually varying titanium chromium nitride compound Hard films and the selection of substrate negative voltage that determines, in the first half section time of deposition, substrate negative voltage selects-180 ~-200 Volt, at the latter half of deposition, substrate negative voltage selects at-120 ~-130 volts；
12) control of coating chamber temperature: refer to the plating determined for obtaining composition continually varying titanium chromium nitride composite ganoine film Film room temperature limits, and for high speed steel substrate, coating chamber temperature not can exceed that 380 degrees Celsius；For hard alloy substrate, plated film Room temperature not can exceed that 420 degrees Celsius；
13) work rest rotary plating: be slowly heated baking at coating chamber, matrix is carried out ion bom bardment, plating titanium chrome alloy mistake Cross layer, composition continually varying titanium chromium nitride composite ganoine film deposition whole during be always maintained at work rest rotate, turn Speed is 6 revs/min.
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