CN106048518A - Preparation method of metal nitride composite hard film - Google Patents

Preparation method of metal nitride composite hard film Download PDF

Info

Publication number
CN106048518A
CN106048518A CN201610555562.1A CN201610555562A CN106048518A CN 106048518 A CN106048518 A CN 106048518A CN 201610555562 A CN201610555562 A CN 201610555562A CN 106048518 A CN106048518 A CN 106048518A
Authority
CN
China
Prior art keywords
arc
aluminum
film
deposition
titanium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610555562.1A
Other languages
Chinese (zh)
Other versions
CN106048518B (en
Inventor
张钧
孙丽婷
王宇
戴步实
赵微
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Taisin Coating Technology Co ltd
Original Assignee
Shenyang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang University filed Critical Shenyang University
Priority to CN201610555562.1A priority Critical patent/CN106048518B/en
Publication of CN106048518A publication Critical patent/CN106048518A/en
Application granted granted Critical
Publication of CN106048518B publication Critical patent/CN106048518B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/50—Substrate holders
    • C23C14/505—Substrate holders for rotation of the substrates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

The invention discloses a preparation method of a metal nitride composite hard film, 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-aluminum-zirconium 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 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 method of metal nitride composite ganoine film.
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 metal nitride composite ganoine film, this method ensure that film layer Composition almost linear consecutive variations from metallic matrix to film surface, reduces in film layer component difference interface due to composition transfer The internal stress caused relatively greatly, thus realize while ensure that high adhesion force, high rigidity and highly heatproof and shockproof, and have good Stability.
The technical scheme is that the preparation method of a kind of metal nitride composite ganoine film includes successively:
1, the determination of deposition technique: determine that multi-arc ion coating is as composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Technology of preparing.
2, the determination of arc source target: determine titanium-aluminum alloy target and pure zirconium target that Ti/Al atomic ratio is (46-50)/(54-50) Equal amount combine as plated film arc source target, or, Al/Ti atomic ratio be 55/45 aluminum titanium alloy target and Ti/Zr atomic ratio be The titanium-zirconium alloy target equal amount of 50/50 combines 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 ensureing membrane uniformity, according to the compound mode in method step 2 at least Select two differing heights different azimuth and become the arc source starting the arc simultaneously of 90 degree of configurations, 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: 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 for obtain composition continually varying titanium-aluminum-zirconium nitride composite ganoine film and from Son 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 as acquisition composition continually varying titanium-aluminum-zirconium nitride composite ganoine film The ion bom bardment technique carried out before plating Mallory sharton alloy transition zone, when coating chamber back end vacuum reaches 8.0 × 10-3 Handkerchief, prebake conditions temperature reach to be filled with argon when 200 DEG C, make coating chamber pressure reach 2.2 × 10-1Handkerchief-2.8 × 10-1Handkerchief, opens Open each arc source, allow the restrictive condition of temperature according to arc source target size size and matrix, keep arc current stable at 50-80 Certain current value between An Pei, carries out ion bom bardment 15 minutes, and bombardment bias progressively increases to 400 volts from 350 volts.
7, the determination of the preparation technology of Mallory sharton alloy transition zone: the ar pressure in coating chamber is maintained at 2.2 × 10-1 Handkerchief ~ 2.8 × 10-1Handkerchief, the titanium-aluminum alloy target of equal amount combination and pure zirconium target, or, the aluminum titanium alloy target of equal amount combination And certain current value that the arc current of titanium-zirconium alloy target is placed between 50-80 ampere, substrate negative voltage is-200 volts, during the starting the arc Between be 10 minutes, then regulation ar pressure reach 2.8 × 10-1Handkerchief, is ready for composition continually varying titanium-aluminum-zirconium nitride The deposition of composite ganoine film.
8, the determination of sedimentation time: refer to determine for obtaining composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Sedimentation time, according to the number in the multi-arc ion coating arc source used and determines whole sedimentation time to the thickness requirement of film layer, Then whole sedimentation time being divided into 3:1, the first half section time wherein deposited is the 3/4 of total sedimentation time, the second half section of deposition Time is 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 the nitridation of composition continually varying titanium aluminum zirconium Thing 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, Ensure that nitrogen partial pressure uniform speed increases, and simultaneously reduce partial pressure of ar gas accordingly by Flow-rate adjustment so that in deposition process two The total pressure of person remains 2.8 × 10-1Handkerchief is constant, and at the end of this stage, nitrogen partial pressure reaches 2.8 × 10-1Handkerchief, argon Dividing potential drop reduces to 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 composition continually varying titanium aluminum zirconium nitrogen Compound 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 used Arc current consistent with aforesaid method step 6, at the latter half of deposition, adjust arc source target arc current, each arc source target Arc current increase 2-4 ampere, until deposition process terminates.
The determination of 11 substrate negative voltage corresponding with sedimentation time: refer to as obtaining the nitridation of composition continually varying titanium aluminum zirconium Thing composite ganoine film and the selection of substrate negative voltage that determines, in the first half section time of deposition, substrate negative voltage select- 180--200 lies prostrate, and at the latter half of deposition, substrate negative voltage selects to lie prostrate at-120--130.
12, the control of coating chamber temperature: refer to as acquisition composition continually varying titanium-aluminum-zirconium nitride composite ganoine film true Fixed coating chamber temperature limiting, for high speed steel substrate, coating chamber temperature not can exceed that 380 degrees Celsius；For carbide matrix Body, 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, plating titanium aluminum zirconium Alloy transition layer, composition continually varying titanium-aluminum-zirconium nitride composite ganoine film deposition whole during be always maintained at work rest Rotating, rotating speed is 6 revs/min.
According to the preparation method of composition continually varying titanium-aluminum-zirconium nitride composite ganoine film proposed by the invention, permissible Obtain above-mentioned composition continually varying titanium-aluminum-zirconium nitride composite ganoine film, this composite ganoine film ensure that membranous layer ingredient from Metallic matrix, to the almost linear consecutive variations of film surface, particularly ensure that N element content is from metallic matrix to film surface Almost linear increase continuously, film layer is formed without component difference interface, thus ensure that high adhesion force, high rigidity and highly heatproof and shockproof While realize, reduce film layer internal stress, and there is good stability.
Compared with the existing technology, present invention determine that multi-arc ion coating is multiple as composition continually varying titanium-aluminum-zirconium nitride Close hard films technology of preparing, it is determined that target material composition, quantity and configuration orientation, it is determined that the selection of metallic matrix to be coated with Pre-treating technology, pre-Bombardment and cleaning technique, the preparation technology of Mallory sharton 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 directrix from metallic matrix to film surface Property consecutive variations, reduces the internal stress that the component difference interface formed in film layer is caused due to composition large change, from And ensure that and realize while high adhesion force, high rigidity and highly heatproof and shockproof and there is good stability, thus advantageously in Improve the friction durability of titanium-aluminum-zirconium nitride composite ganoine film, be more suitable for the application at industrial circle.
Detailed description of the invention
Embodiment 1
Prepared composition continually varying titanium-aluminum-zirconium nitride composite ganoine film on commercial high speed steel W18Cr4V, its method is:
1, the determination of deposition technique: determine that multi-arc ion coating is as composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Technology of preparing.
2, the determination of arc source target: determine titanium-aluminum alloy target and pure zirconium target equal amount group that Ti/Al atomic ratio is 50/50 Cooperation is 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 ensureing membrane uniformity, select 2 titanium-aluminum alloy targets and 2 zirconium target conducts Arc source, and, every pair of target, i.e. 1 titanium-aluminum alloy target and 1 zirconium target, it is in differing heights different azimuth and becomes 90 degree of configurations, The starting the arc simultaneously, and to ensure simultaneously high speed steel substrate to be coated coating chamber whole during, coating chamber temperature be less than base The temperature that body allows.
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 for obtain composition continually varying titanium-aluminum-zirconium nitride composite ganoine film and from Son 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 as acquisition composition continually varying titanium-aluminum-zirconium nitride composite ganoine film The ion bom bardment technique carried out before plating alloy transition zone, when coating chamber back end vacuum reaches 8.0 × 10-3Handkerchief, preliminary drying Roasting 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 current Stablizing at 56 amperes, carry out ion bom bardment 15 minutes, bombardment bias progressively increases to 400 volts from 350 volts.
7, the determination of the preparation technology of Mallory sharton alloy transition zone: the ar pressure in coating chamber is maintained at 2.5 × 10-1 Handkerchief, the arc current of 2 titanium-aluminum alloy targets and 2 zirconium targets is placed in 56 amperes, and substrate negative voltage is-200 volts, and arcing time is 10 Minute, then regulation ar pressure reaches 2.8 × 10-1Handkerchief, is ready for composition continually varying titanium-aluminum-zirconium nitride compound hard The deposition of plasma membrane.
8, the determination of sedimentation time: refer to determine for obtaining composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Sedimentation 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 minutes, then whole sedimentation time being divided into two parts, the first half section time wherein deposited is 60 minutes, the second half section of deposition Time is 20 minutes.
The control of the 9 reacting gas dividing potential drops corresponding with sedimentation time: refer to as obtaining the nitridation of composition continually varying titanium aluminum zirconium Thing 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, Ensure that nitrogen partial pressure uniform speed increases, and simultaneously reduce partial pressure of ar gas accordingly by Flow-rate adjustment so that in deposition process two The total pressure of person remains 2.8 × 10-1Handkerchief is constant, and at the end of this stage, nitrogen partial pressure reaches 2.8 × 10-1Handkerchief, argon Dividing potential drop reduces to 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 the nitridation of composition continually varying titanium aluminum zirconium 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, and the arc current of each arc source target is stable at 56 amperes, at the latter half of deposition, adjusts Whole 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 the nitridation of composition continually varying titanium aluminum zirconium Thing 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 Volt, at the latter half of deposition, substrate negative voltage selects at-120 volts.
12, the control of coating chamber temperature: refer to as acquisition composition continually varying titanium-aluminum-zirconium nitride composite ganoine film true Fixed coating chamber temperature limiting, in the present embodiment, coating chamber temperature maximum is 302 degrees Celsius.
13, work rest rotary plating: be slowly heated baking at coating chamber, matrix is carried out ion bom bardment, plating titanium aluminum zirconium Alloy transition layer, composition continually varying titanium-aluminum-zirconium nitride composite ganoine film deposition whole during be always maintained at work rest Rotating, rotating speed is 6 revs/min.
To making the composition continually varying titanium-aluminum-zirconium nitride composite ganoine film prepared in aforementioned manners be measured, its film Layer thickness is 2.5 microns, this composite ganoine film membranous layer ingredient almost linear consecutive variations from high speed steel substrate to film surface, film In Ceng, N element content almost linear from high speed steel substrate to film surface increases continuously, and does not occur component difference circle in film layer Face, it is ensured that realize while high adhesion force, high rigidity and highly heatproof and shockproof.
Embodiment 2
Prepared composition continually varying titanium-aluminum-zirconium nitride composite ganoine film on hard alloy YT15 matrix, its method is:
1, the determination of deposition technique: determine that multi-arc ion coating is as composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Technology of preparing.
2, the determination of arc source target: determine that aluminum titanium alloy target that Al/Ti atomic ratio is 55/45 and Ti/Zr atomic ratio are 50/ The titanium-zirconium alloy target equal amount of 50 combines 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 ensureing membrane uniformity, select 2 aluminum titanium alloy targets and 2 titanium-zirconium alloy Target as arc source, and, every pair of target, i.e. 1 aluminum titanium alloy target and 1 titanium-zirconium alloy target, be in differing heights different azimuth and Become 90 degree of configurations, the starting the arc simultaneously, and to ensure simultaneously hard alloy substrate to be coated coating chamber whole during, coating chamber The temperature that temperature allows less than matrix.
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 for obtain composition continually varying titanium-aluminum-zirconium nitride composite ganoine film and from Son 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 as acquisition composition continually varying titanium-aluminum-zirconium nitride composite ganoine film The ion bom bardment technique carried out before plating Mallory sharton alloy transition zone, when coating chamber back end vacuum reaches 8.0 × 10-3 Handkerchief, prebake conditions temperature reach to be filled with argon when 200 DEG C, make coating chamber pressure reach 2.5 × 10-1Handkerchief, opens each arc source, root According to arc source target size size, keeping arc current to stablize at 58 amperes, carry out ion bom bardment 15 minutes, bombardment bias is from 350 volts Progressively increase to 400 volts.
7, the determination of the preparation technology of Mallory sharton alloy transition zone: the ar pressure in coating chamber is maintained at 2.5 × 10-1 Handkerchief, the arc current of 4 titanium-zirconium alloy 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 the heavy of composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Long-pending.
8, the determination of sedimentation time: refer to determine for obtaining composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Sedimentation 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 minutes, then whole sedimentation time being divided into two parts, the first half section time wherein deposited is 60 minutes, the second half section of deposition Time is 20 minutes.
The control of the 9 reacting gas dividing potential drops corresponding with sedimentation time: refer to as obtaining the nitridation of composition continually varying titanium aluminum zirconium Thing 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, Ensure that nitrogen partial pressure uniform speed increases, and simultaneously reduce partial pressure of ar gas accordingly by Flow-rate adjustment so that in deposition process two The total pressure of person remains 2.8 × 10-1Handkerchief is constant, and at the end of this stage, nitrogen partial pressure reaches 2.8 × 10-1Handkerchief, argon Dividing potential drop reduces to 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 the nitridation of composition continually varying titanium aluminum zirconium 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 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 the nitridation of composition continually varying titanium aluminum zirconium Thing composite ganoine film and the selection of substrate negative voltage that determines, in the first half section time of deposition, substrate negative voltage selects-200 Volt, at the latter half of deposition, substrate negative voltage selects at-130 volts.
12, the control of coating chamber temperature: refer to as acquisition composition continually varying titanium-aluminum-zirconium nitride composite ganoine film true Fixed 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, plating titanium aluminum zirconium Alloy transition layer, composition continually varying titanium-aluminum-zirconium nitride composite ganoine film deposition whole during be always maintained at work rest Rotating, rotating speed is 6 revs/min.
To making the composition continually varying titanium-aluminum-zirconium 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 hard alloy substrate to film surface, In film layer, N element content almost linear from hard alloy substrate to film surface increases continuously, and does not occur that composition is poor in film layer Different 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 metal nitride composite ganoine film, it is characterised in that described method includes procedure below:
1) determination of deposition technique: determine that multi-arc ion coating is as composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Technology of preparing；
2) determination of arc source target: determine that titanium-aluminum alloy target that Ti/Al atomic ratio is (46-50)/(54-50) and pure zirconium target are equal Number combinations as plated film arc source target, or, Al/Ti atomic ratio be 55/45 aluminum titanium alloy target and Ti/Zr atomic ratio be 50/ The titanium-zirconium alloy target equal amount of 50 combines as plated film arc source target；
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 according to the compound mode in method step 2 The arc source starting the arc simultaneously of two differing heights different azimuth and one-tenth 90 degree configuration, and to ensure that metallic matrix to be coated is in plating simultaneously Film room whole during, coating chamber temperature less than matrix allow temperature；
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 bang at ion for obtaining composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Hit the heated baking technique that technique starts to carry out before, reach 3 × 10 in coating chamber vacuum-2During handkerchief, start baking electric current, For avoiding thermal stress to gather, using 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 plating for obtaining composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Cover the ion bom bardment technique carried out before Mallory sharton 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, allows the restrictive condition of temperature according to arc source target size size and matrix, keep arc current stable 50-80 ampere it Between certain current value, carry out ion bom bardment 15 minutes, bombardment bias progressively increase to 400 volts from 350 volts；
7) determination of the preparation technology of Mallory sharton alloy transition zone: the ar pressure in coating chamber is maintained at 2.2 × 10-1Handkerchief- 2.8×10-1Handkerchief, equal amount combination titanium-aluminum alloy target and pure zirconium target, or, equal amount combination aluminum titanium alloy target and The arc current of titanium-zirconium alloy target is placed in certain current value between 50-80 ampere, and substrate negative voltage is-200 volts, arcing time Being 10 minutes, then regulation ar pressure reaches 2.8 × 10-1Handkerchief, is ready for composition continually varying titanium-aluminum-zirconium nitride multiple Close the deposition of hard films；
8) determination of sedimentation time: refer to the deposition determined for obtaining composition continually varying titanium-aluminum-zirconium nitride composite ganoine film Time, the number according to the multi-arc ion coating arc source used and the thickness requirement to film layer determine whole sedimentation time, then Whole sedimentation time is divided into 3:1, and the first half section time wherein deposited is the 3/4 of total sedimentation time, the latter half of deposition For total sedimentation time 1/4；
9) control of corresponding with sedimentation time reacting gas dividing potential drop: refer to as obtaining composition continually varying titanium-aluminum-zirconium nitride multiple The reacting gas nitrogen partial pressure closing hard films and determine controls process, passes through Flow-rate adjustment in the first half section time of deposition, it is ensured that Nitrogen partial pressure uniform speed increases, and simultaneously reduces partial pressure of ar gas accordingly by Flow-rate adjustment so that in deposition process the two 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 Reducing to 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-aluminum-zirconium 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 of the arc source target 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 ~ 4 amperes, until deposition process terminates；
11) determination of the substrate negative voltage corresponding with sedimentation time: refer to as obtaining composition continually varying titanium-aluminum-zirconium nitride multiple The selection of the substrate negative voltage closing hard films and determine, in the first half section time of deposition, substrate negative voltage selects at-180--200 Volt, at the latter half of deposition, substrate negative voltage selects to lie prostrate at-120--130；
12) control of coating chamber temperature: refer to determine for obtaining composition continually varying titanium-aluminum-zirconium 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, plating 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 Mallory sharton alloy Transition zone, composition continually varying titanium-aluminum-zirconium nitride composite ganoine film deposition whole during be always maintained at work rest rotation Turning, rotating speed is 6 revs/min.
CN201610555562.1A 2016-07-15 2016-07-15 A kind of preparation method of metal nitride composite ganoine film Active CN106048518B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610555562.1A CN106048518B (en) 2016-07-15 2016-07-15 A kind of preparation method of metal nitride composite ganoine film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610555562.1A CN106048518B (en) 2016-07-15 2016-07-15 A kind of preparation method of metal nitride composite ganoine film

Publications (2)

Publication Number Publication Date
CN106048518A true CN106048518A (en) 2016-10-26
CN106048518B CN106048518B (en) 2019-02-22

Family

ID=57186838

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610555562.1A Active CN106048518B (en) 2016-07-15 2016-07-15 A kind of preparation method of metal nitride composite ganoine film

Country Status (1)

Country Link
CN (1) CN106048518B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108950488A (en) * 2018-08-03 2018-12-07 河北工程大学 TiAl/TiAlN/TiZrAlN composite coating and preparation method thereof
CN113088895A (en) * 2021-04-01 2021-07-09 九牧厨卫股份有限公司 Decorative low-temperature hard coating and coating method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210309A (en) * 2006-12-30 2008-07-02 沈阳大学 Method for preparing (TiAlZr)N ultra-hard coating by employing multiple arc ion plating
US20090068450A1 (en) * 2005-07-15 2009-03-12 Wolf-Dieter Muenz Method and Apparatus for Multi-Cathode PVD Coating and Substrate with PVD Coating
CN101709450A (en) * 2009-11-30 2010-05-19 沈阳大学 Method for preparing zirconium-titanium-aluminum-nitrogen nitride gradient hard reaction film
CN103572220A (en) * 2013-10-28 2014-02-12 沈阳大学 Method for preparing nitrogen0gradient hard reaction membrane of titanium aluminum niobium nitride (TiAlNbN)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090068450A1 (en) * 2005-07-15 2009-03-12 Wolf-Dieter Muenz Method and Apparatus for Multi-Cathode PVD Coating and Substrate with PVD Coating
CN101210309A (en) * 2006-12-30 2008-07-02 沈阳大学 Method for preparing (TiAlZr)N ultra-hard coating by employing multiple arc ion plating
CN101709450A (en) * 2009-11-30 2010-05-19 沈阳大学 Method for preparing zirconium-titanium-aluminum-nitrogen nitride gradient hard reaction film
CN103572220A (en) * 2013-10-28 2014-02-12 沈阳大学 Method for preparing nitrogen0gradient hard reaction membrane of titanium aluminum niobium nitride (TiAlNbN)

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
吕会敏: "（Ti,Al,Zr）N多元氮梯度硬质反应膜的组织结构和性能", 《材料研究学报》 *
张钧: "《多弧离子镀技术与应用》", 31 December 2007, 冶金工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108950488A (en) * 2018-08-03 2018-12-07 河北工程大学 TiAl/TiAlN/TiZrAlN composite coating and preparation method thereof
CN113088895A (en) * 2021-04-01 2021-07-09 九牧厨卫股份有限公司 Decorative low-temperature hard coating and coating method and application thereof

Also Published As

Publication number Publication date
CN106048518B (en) 2019-02-22

Similar Documents

Publication Publication Date Title
CN106011752B (en) A kind of preparation method of metal hard films
CN101230448B (en) Method for preparing multi-arc ion plating aluminium titanium chrome silicon yttrium nitride multi-component ultra-hard reaction film
CN101709450B (en) Method for preparing zirconium-titanium-aluminum-nitrogen nitride gradient hard reaction film
CN101705471B (en) Preparation method of chromium nitride titanium aluminum nitrogen gradient hard reaction film
CN103572220B (en) A kind of preparation method of TiAlN niobium nitrogen gradient hard reaction film
CN108950488A (en) TiAl/TiAlN/TiZrAlN composite coating and preparation method thereof
CN106011753B (en) A kind of preparation method of metal composite hard films
CN106048539B (en) A kind of preparation method of Titanium aln precipitation composite ganoine film
CN101210309A (en) Method for preparing (TiAlZr)N ultra-hard coating by employing multiple arc ion plating
CN107557736A (en) A kind of AlCrSiVN nano-composite coatings and preparation method thereof
CN103866243B (en) A kind of preparation method of nitrogen oxygen titanium aluminium/TiAlN/titanium aluminum composite membrane
CN106048525A (en) Preparation method of titanium-chromium metal nitride composite hard film with continuous change
CN101591766B (en) Method for preparing titanium-aluminum-zirconium nitride multicomponent hard reaction gradient film
CN101591765B (en) Method for preparing chromium-titanium-aluminum-zirconium nitride multicomponent hard reaction gradient film
CN106048518A (en) Preparation method of metal nitride composite hard film
CN103556119B (en) A kind of preparation method of titanium nitride zirconium niobium nitrogen gradient hard reaction film
CN104726823A (en) Method for preparation of titanium aluminum zirconium niobium/titanium aluminum zirconium niobium nitride quaternary-nitrogen gradient films
CN109023263A (en) TiAl/TiAlN/TiCrAlN composite coating and preparation method thereof
CN104451560A (en) Preparation method of (TiAlZrNb)N nitrogen gradient imitation gold decorative film
CN103572219A (en) Method for preparing nitrogen-gradient hard reaction membrane of chromium titanium niobium nitride (CrTiNbN)
CN107217238A (en) A kind of preparation method of titanium-aluminum-zirconium nitride plated film carbide drill
CN104328384A (en) Preparation method of reaction titanium aluminum zirconium niobium nitride nitrogen-gradient hard reaction film
CN106048540B (en) The preparation method of the titanium zirconium metal nitride composite ganoine film of ingredient consecutive variations
CN103911591B (en) A kind of preparation method of high adhesive force nitrogen oxygen titanium aluminium/titanium aluminum composite membrane
CN114411098A (en) Coating method of TiNb coating

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230506

Address after: Room 106, Building 1, No. 692, Dalingshan Section, Shida Road, Dalingshan Town, Dongguan City, Guangdong Province, 523809

Patentee after: DONGGUAN TAISIN COATING TECHNOLOGY CO.,LTD.

Address before: 110044 Liaoning Province, Shenyang City District wanghuanan Street No. 21

Patentee before: SHENYANG University