CN106676470A - AlTiON hot work die steel composite gradient coating and preparation method thereof - Google Patents

AlTiON hot work die steel composite gradient coating and preparation method thereof Download PDF

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CN106676470A
CN106676470A CN201710013233.9A CN201710013233A CN106676470A CN 106676470 A CN106676470 A CN 106676470A CN 201710013233 A CN201710013233 A CN 201710013233A CN 106676470 A CN106676470 A CN 106676470A
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altion
crn
altin
coating
layer
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CN106676470B (en
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马立安
魏朝晖
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Fujian University of Technology
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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
    • C23C14/0676—Oxynitrides
    • 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
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • 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

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  • 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)

Abstract

The invention discloses an AlTiON hot work die steel composite gradient coating and a preparation method thereof. The preparation method of the coating comprises five continuous stages that (1) a bonding layer CrN thin film is deposited on a hot work die steel base body; (2) CrN supporting layer and AlTiN supporting layer are periodically and alternately deposited on a CrN bonding layer base; (3) O2 and N2 are injected into a furnace chamber simultaneously, the flow of the injected O2 is linearly increased, the flow of the injected N2 is linearly decreased, the chamber pressure is kept to be constant, and an AlTiON gradient layer is manufactured; (4) the flow of the N2 and O2 is kept to be constant, and an AlTiON functional layer is manufactured; and (5) a CrN/AlTiN/AlTiON composite gradient layer is subjected to high-temperature on-spot annealing in a vacuum chamber. The AlTiON gradient coating has high binding force with the base body, high tenacity, low internal stress, high hardness and high abrasive resistance are achieved, and meanwhile, high-temperature oxidation resistance and thermal fatigue resistance are achieved as well.

Description

A kind of AlTiON hot die steels complex gradient coating and preparation method thereof
Technical field
The invention provides a kind of manufacture method of nano combined gradient layer, belongs to field of surface engineering technique, specifically relate to And a kind of AlTiON hot die steels complex gradient coating and preparation method thereof.
Background technology
Die cast is the method for the molding precision metal detail under high temperature, high speed, condition of high voltage.Hot die steel is because of it Die casting manufacture is widely used in good fatigue resistance, non-oxidizability, corrosion resistance, wearability, due to die casting Use condition is extremely severe, and during mould is actually used, Jing often results in initial failure before die life termination.Failure The cracking that mainly abrasion, burn into fusion, adhesion and heat exhaustion cause.Can not be expired by developing high performance hot-work die steel Foot further improves hot die steel service life.In order to improve, the country such as hot die steel service life, America and Europe is main to be adopted Surface-coating technology prepares wear-resisting, antioxidation and corrosion-resistant finishes to improve service life in hot die steel mold cavity surface.
Extend its life-span in surface of hot die steel deposition solid-ceramic coating using PVD technique becomes and grinds in recent years Study carefully focus.Coating structure and coating composition are more to CrN, ZrN, TiAlN, AlTiN, TiAlON etc. from the single tin of relatively early exploitation First composite coating development.These ceramic coatings deposited using PVD technique are although with higher hardness, wearability and good The advantages of chemical stability.But some each limitation and drawbacks are still suffered from, the die casting life-span upgrading of ceramic coating is made It is restricted.Such as TiAlN because its dislocation motion is limited, the relatively low TiAlN coatings that easily cause of coating toughness are shelled using process laminate From failure；Again such as：The AlTiN composite coatings high temperature oxidation resistance of high Al content is preferable, but with Al in preparation process The raising Al of content easily forms soft hexagonal phase AlN with N element, reduces the mechanical property such as hardness, the elastic modelling quantity of coating Energy；Again such as：The introducing of O high-temperature oxidation resistance compared with AlTiN coatings is improved in TiAlON coatings, but TiAlON is applied Layer internal stress is higher, and inter-layer bonding force is poor, and hardness is low, thermal fatigue resistance fail to obtain the problems such as being obviously improved compel it is to be solved.
For existing PVD（Including arc ion plating and sputtering plating）The TiAlON coating process of preparation its shortcoming mainly has：
1. the monolayer TiAlON coatings that prepared by PVD are poor with basal body binding force（Less than 20N）, and with CrN make transition zone or with TiAl makees the TiAlON composite coatings of transition zone preparation can effectively improve film-substrate cohesion, but interlayer internal stress is larger, tough The low, coating of property is easily peeled off；
2. TiAlON coating hardness is relatively low, wearability and resistance to high temperature oxidation and thermal fatigue resistance are poor.
The content of the invention
The present invention is directed to the deficiencies in the prior art, there is provided a kind of surface of hot die steel AlTiON gradient coatings and its making Method, the adhesion between the AlTiON gradient coatings and matrix is big, with high tenacity, low internal stress, high rigidity, and high-wearing feature, Have high-temperature oxidation resistant and thermal fatigue resistance concurrently simultaneously.
For achieving the above object, the present invention is adopted the following technical scheme that：
Using cathode arc ion plating technique in hot die steel such as：Make CrN/AlTiN/AlTiON on the matrixes such as H11, H13 to answer Close gradient layer.2 pure Cr（99.99%）Target and 2 AlTi（99.9%）Target（Al :Ti ratios are 67:33）To arranged In PVD inner chambers, to ensure alternating deposit CrN/AlTiN supporting layers.The coating manufacturing process is divided into continuous five stages：First Stage is in hot die steel substrate deposit tack coat CrN thin film；Second stage cycle alternating deposit on the basis of CrN tack coats CrN/AlTiN supporting layers；Phase III is passed through O simultaneously into furnace chamber2And N2And make to be passed through O2Flow linear rise, N2Flow line Property decline, keep the constant making AlTiON gradient layers of chamber pressure；Fourth stage keeps N2And O2The constant making AlTiON of flow Functional layer；The high-temp in-situ annealing in vacuum cavity of 5th stage CrN/AlTiN/AlTiON complex gradient layer.Each stage is thin The length of film sedimentation time is determined by required coating layer thickness.
Deposition parameter is as follows：
Step 1：The substrate for cleaning up is fixed on the carrier of coating chamber, the distance of target to substrate is about 22cm, is opened Mechanical pump and molecular pump evacuation make cavity background vacuum be less than 3 × 10-4Pa, opens heating system, is warming up to 200 ~ 450 °C, opening carrier makes its 2 ~ 8 r/min rotational speed, and Ar 200 ~ 320SCCM of gas are passed through into cavity room, adjusts vacuum chamber Pressure is 0.3 ~ 2 Pa, and substrate adds 600 ~ 800V back bias voltages, opens 2 pure Cr targets, and target current is 50 ~ 120A, to substrate Carry out the min of Glow Discharge Cleaning 10 ~ 20;Adjustment negative bias is depressed into 50 ~ 200V, and 2 Cr target currents are adjusted to 50 ~ 90A, subsequently Turn off Ar air valves while opening N2To 250 ~ 350 SCCM, adjustment vacuum chamber pressure is that 1 ~ 3Pa deposits CrN tack coats to throughput valve About 4 ~ 10 min；
Step 2：Depositing support layer CrN/AlTiN;
Adjustment N2To 380 ~ 450SCCM, 2 pure Cr target currents are adjusted to 60 ~ 110A to throughput, open 2 AlTi target currents 55 ~ 115A is adjusted to, carrier keeps the min of 2 ~ 8 r/min rotational speed alternating deposit supporting layers CrN/AlTiN about 30 ~ 60;
Step 3：Sedimentation gradient layer AlTiON；
O is passed through within the time period while into cavity2And N2Gas, keeps 2 AlTi 55 ~ 115A of target current constant, cavity temperature Degree is controlled at 200 ~ 450 °C, as coating carries out N2Tolerance is from 380 ~ 450SCCM uniform descents to 340 ~ 410 SCCM, O2Stream Amount at the uniform velocity rises to 25 ~ 35 SCCM, the min of depositing Al TiON gradient layer about 15 ~ 25 from 0 SCCM;
Step 4:Deposit functional layers AlTiON；
The stage continues to be passed through O to cavity2And N2Gas, is maintained at step 3 finishing phase N2And O2The constant i.e. N of throughput2Throughput For 340 ~ 410 SCCM, O2Throughput is 25 ~ 35SCCM, and 2 AlTi target currents are 55 ~ 115A, and deposit functional layers AlTiON is about 15~30min;
Step 5：Complex gradient layer CrN/AlTiN/AlTiON high-temp in-situ annealing in vacuum cavity.
Turn off 2 AlTi target currents, turn off O2And N2Gas flow valve, chamber vacuum degree is adjusted to 4 × 10-3 Pa, substrate Temperature is heated to 650 ~ 850 °C, and 3 ~ 5h of insulation makes multi-gradient film CrN/AlTiN/AlTiON high-temp in-situs in vacuum cavity Annealing.
Difference from prior art is：1. what is made is the compound paintings of AlTiON of hot die steel high aluminium content Layer, coating composition is made up of tack coat CrN, supporting layer CrN/AlTiN, gradient layer AlTiON and functional layer AlTiON；2. prop up Support layer CrN/AlTiN is effectively to inhibit column crystal to grow by cycle alternating deposit CrN/AlTiN plural layers so that The CrN/AlTiN thin film of deposition is finer and close；And gradient coating AlTiON prepare be by being passed through gas in N/O ratios gradient connect Continuous change shows that residual stress is little changing membranous layer ingredient compared with non-uniform components thin film, and adhesion strength is big and toughness is high Advantage；3. AlTiON functional layers be made by step 4 and step 5 is completed, composite coating high temperature is former wherein in step 5 On the one hand position annealing reduce inter-laminar stress, improves shock proof toughness and thermal fatigue resistance between thin film；Another aspect high temperature Annealing makes top layer AlTiON surface in situ generate γ-Al2O3Tissue is so as to greatly improving the hardness of AlTiON coatings, wear-resisting Property and high-temperature oxidation resistant and resistance to corrosion.
The AlTiON gradient layers of making have the advantage that：
1. the AlTiON gradient coatings that the present invention is developed have higher hardness, and wearability and corrosion resistance and good.
2. the AlTiON gradient coatings that the present invention is developed have higher high high-temp stability and fatigue resistance, can be used for Die casting manufacture field.
3. the present invention is developed AlTiON gradient coatings thickness is uniform, compact structure and matrix have good combination strong Degree.
Description of the drawings
Fig. 1 is the surface shape of the AlTiON complex gradient coatings prepared using arc ion plating (aip) in the present embodiment 2 Looks.
Fig. 2 is Al, Ti, O, the N for the AlTiON complex gradient coatings prepared using arc ion plating (aip) in the present embodiment 2 XPS spectrum figure.
Fig. 3 is the AlTiON complex gradient coating wear profiles prepared using arc ion plating (aip) in the present embodiment 2.
Specific embodiment
In order that content of the present invention easily facilitates understanding, with reference to specific embodiment to of the present invention Technical scheme is described further, but the present invention is not limited only to this.
A kind of AlTiON hot die steels complex gradient coating, has been sequentially depositing between substrate surface and AlTiON functional layers Tack coat CrN, supporting layer CrN/AlTiN, gradient layer AlTiON, wherein supporting layer CrN/AlTiN are alternately heavy by CrN, AlTiN Product makes.
A kind of preparation method of AlTiON hot die steels complex gradient coating, the coating is by ion arc PVD deposition system It is standby, comprise the following specific steps that：
Step 1：The substrate for cleaning up is fixed on the carrier of coating chamber, carrier rotating speed is controlled in 2 ~ 8 r/min, cavity temperature Degree control is passed through Ar 200 ~ 320SCCM of gas at 200 ~ 450 °C in cavity room, pressure in vacuum tank is 0.3 ~ 2 Pa, and substrate adds 600 ~ 800V back bias voltages, Cr target currents are controlled in 50 ~ 120A, and the min of Glow Discharge Cleaning 10 ~ 20 is carried out to substrate;Adjustment Negative bias added by substrate is depressed into 50 ~ 200V, and Cr target currents are adjusted to 50 ~ 90A, turns off Ar air valves while opening N2Throughput valve is extremely 250 ~ 350 SCCM, adjustment vacuum chamber pressure is the min of 1 ~ 3Pa deposition CrN tack coats 4 ~ 10；
Step 2：Adjustment N2To 380 ~ 450SCCM, Cr target currents are adjusted to 60 ~ 110A to throughput, and AlTi target currents are adjusted to 55 ~ 115A, alternating deposit supporting layer CrN/AlTiN 30 ~ 60 min;
Step 3：Cr target currents are closed, into cavity O is passed through2And N2Gas, keeps AlTi 55 ~ 115A of target current constant, cavity temperature Degree is controlled at 200 ~ 450 °C, as coating carries out N2Throughput is from 380 ~ 450SCCM uniform descents to 340 ~ 410 SCCM, O2 Throughput at the uniform velocity rises to 25 ~ 35 SCCM, the min of depositing Al TiON gradient layer 15 ~ 25 from 0 SCCM;
Step 4:Continue to be passed through O to cavity2And N2Gas, is maintained at step 3 finishing phase N2And O2Throughput is constant, AlTi targets electricity Flow constant, deposit functional layers 15 ~ 30min of AlTiON;
Step 5:Stop plated film, chamber vacuum degree is adjusted to 4 × 10-3 Pa, substrate temperature is heated to 650 ~ 850 °C, and insulation 3 ~ 5h high-temp in-situs are annealed.
Embodiment 1
CrN/AlTiN/AlTiON complex gradient layers are made on hot die steel H11 matrixes using cathode arc ion plating technique. 2 pure Cr（99.99%）Target and 2 AlTi（99.9%）Target（Al :Ti ratios are 67:33）To arranged in PVD inner chambers, To ensure alternating deposit CrN/AlTiN supporting layers.The coating manufacturing process is divided into continuous five stages：First stage is in heat work Tack coat CrN thin film is deposited in mould steel matrix；Second stage cycle alternating deposit CrN/AlTiN on the basis of CrN tack coats Supporting layer；Phase III is passed through O simultaneously into furnace chamber2And N2And make to be passed through O2Flow linear rise, N2Flow linear decline, protects Hold the constant making AlTiON gradient layers of chamber pressure；Fourth stage keeps N2And O2The constant making AlTiON functional layers of flow；The The high-temp in-situ annealing in vacuum cavity of five stage CrN/AlTiN/AlTiON complex gradient layers.
Deposition parameter is as follows：
Step 1：The substrate for cleaning up is fixed on the carrier of coating chamber, the distance of target to substrate is 22cm, opens machine Tool pump and molecular pump evacuation make cavity background vacuum be less than 3 × 10-4Pa, opens heating system, is warming up to 200 °C, Opening carrier makes its 2r/min rotational speed, and Ar gas 200SCCM are passed through into cavity room, and adjustment pressure in vacuum tank is 0.3 Pa, substrate adds 600V back bias voltages, opens 2 pure Cr targets, and target current is 50A, to substrate Glow Discharge Cleaning is carried out 10min;Adjustment negative bias is depressed into 50V, and 2 Cr target currents are adjusted to 50A, subsequently turn off Ar air valves while opening N2Throughput valve To 250SCCM, adjustment vacuum chamber pressure is the min of 1Pa deposition CrN tack coats 4；
Step 2：Depositing support layer CrN/AlTiN;
Adjustment N2To 380SCCM, 2 pure Cr target currents are adjusted to 60A to throughput, open 2 AlTi target currents and are adjusted to 55A, Carrier keeps the min of 2r/min rotational speed alternating deposit supporting layers CrN/AlTiN 30;
Step 3：Sedimentation gradient layer AlTiON；
O is passed through within the time period while into cavity2And N2Gas, keeps 2 AlTi target current 55A constant, cavity temperature control Make at 200 °C, as coating carries out N2Tolerance is from 380SCCM uniform descents to 340 SCCM, O2Flow is at the uniform velocity gone up from 0 SCCM It is raised to 25 SCCM, depositing Al TiON gradient layer 15min;
Step 4:Deposit functional layers AlTiON；
The stage continues to be passed through O to cavity2And N2Gas, is maintained at step 3 finishing phase N2And O2The constant i.e. N of throughput2Throughput For 340SCCM, O2Throughput is 25SCCM, and 2 AlTi target currents are 55A, deposit functional layers AlTiON 15min;
Step 5：Complex gradient layer CrN/AlTiN/AlTiON high-temp in-situ annealing in vacuum cavity.
Turn off 2 AlTi target currents, turn off O2And N2Gas flow valve, chamber vacuum degree is adjusted to 4 × 10-3 Pa, substrate Temperature is heated to 650 °C, and insulation 3h makes multi-gradient film CrN/AlTiN/AlTiON high-temp in-situ annealing in vacuum cavity.
Embodiment 2
CrN/AlTiN/AlTiON complex gradient layers are made on hot die steel H13 matrixes using cathode arc ion plating technique. 2 pure Cr（99.99%）Target and 2 AlTi（99.9%）Target（Al :Ti ratios are 67:33）To arranged in PVD inner chambers, To ensure alternating deposit CrN/AlTiN supporting layers.The coating manufacturing process is divided into continuous five stages：First stage is in heat work Tack coat CrN thin film is deposited in mould steel matrix；Second stage cycle alternating deposit CrN/AlTiN on the basis of CrN tack coats Supporting layer；Phase III is passed through O simultaneously into furnace chamber2And N2And make to be passed through O2Flow linear rise, N2Flow linear decline, protects Hold the constant making AlTiON gradient layers of chamber pressure；Fourth stage keeps N2And O2The constant making AlTiON functional layers of flow；The The high-temp in-situ annealing in vacuum cavity of five stage CrN/AlTiN/AlTiON complex gradient layers.
Deposition parameter is as follows：
Step 1：The substrate for cleaning up is fixed on the carrier of coating chamber, the distance of target to substrate is 22cm, opens machine Tool pump and molecular pump evacuation make cavity background vacuum be less than 3 × 10-4Pa, opens heating system, is warming up to 300 °C, Opening carrier makes its 4 r/min rotational speed, and Ar gas 260SCCM are passed through into cavity room, and adjustment pressure in vacuum tank is 1Pa, Substrate adds 700V back bias voltages, opens 2 pure Cr targets, and target current is 80A, the min of Glow Discharge Cleaning 15 is carried out to substrate; Adjustment negative bias is depressed into 100V, and 2 Cr target currents are adjusted to 70A, subsequently turn off Ar air valves while opening N2Throughput valve is extremely 300SCCM, adjustment vacuum chamber pressure is that 2Pa deposits CrN tack coat 7min；
Step 2：Depositing support layer CrN/AlTiN;
Adjustment N2To 400SCCM, 2 pure Cr target currents are adjusted to 80A to throughput, open 2 AlTi target currents and are adjusted to 80A, carrier keeps the min of 5 r/min rotational speed alternating deposit supporting layers CrN/AlTiN 45;
Step 3：Sedimentation gradient layer AlTiON；
O is passed through within the time period while into cavity2And N2Gas, keeps 2 AlTi target current 80A constant, cavity temperature control Make at 300 °C, as coating carries out N2Tolerance from 400SCCM uniform descents to 360SCCM, O2Flow is at the uniform velocity gone up from 0 SCCM It is raised to 30SCCM, depositing Al TiON gradient layer 20min;
Step 4:Deposit functional layers AlTiON；
The stage continues to be passed through O to cavity2And N2Gas, is maintained at step 3 finishing phase N2And O2The constant i.e. N of throughput2Throughput For 360 SCCM, O2Throughput is 30SCCM, and 2 AlTi target currents are 80A, deposit functional layers AlTiON 20min;
Step 5：Complex gradient layer CrN/AlTiN/AlTiON high-temp in-situ annealing in vacuum cavity.
Turn off 2 AlTi target currents, turn off O2And N2Gas flow valve, chamber vacuum degree is adjusted to 4 × 10-3 Pa, substrate Temperature is heated to 700 °C, and insulation 4h makes multi-gradient film CrN/AlTiN/AlTiON high-temp in-situ annealing in vacuum cavity.
Can be seen that the AlTiON coating surfaces of deposition are opposed flattened from the scanning electron microscopic observation of Fig. 1, bulky grain is less, only With the presence of a small amount of white bright drop.
As can be seen from Figure 2 AlTiON complex gradient coatings are elementary composition by tetra- kinds of Al, Ti, O, N；Al2P is understood by 2 (a) analysis Peak occurs in 74.3eV, shows that Al is mainly with AlN and Al2O3Phase composition；Understand Ti elements mainly with TiN by Fig. 2 (b) analyses And TiO2Mutually occur；Analysis Fig. 2 (c) understands that O peaks correspond mainly to TiO2And Al2O3；Analysis Fig. 2 (d) understands that N1s peaks are corresponded to TiN and AlN.
Wear test is completed on CSEM balls-disc type abrasion instrument, and to ball the WC-Co balls of a diameter of 6.0 mm, lotus are adopted Weight is 10N, and sliding distance is set to 800m, is tested under unlubricated state.Can from Fig. 3 AlTiON complex gradient coating wear profiles The coefficient of friction for knowing sample is 0.6 or so, and little coefficient of friction implys that sample has excellent wear resistance.
Embodiment 3
CrN/AlTiN/AlTiON complex gradient layers are made on hot die steel H13 matrixes using cathode arc ion plating technique. 2 pure Cr（99.99%）Target and 2 AlTi（99.9%）Target（Al :Ti ratios are 67:33）To arranged in PVD inner chambers, To ensure alternating deposit CrN/AlTiN supporting layers.The coating manufacturing process is divided into continuous five stages：First stage is in heat work Tack coat CrN thin film is deposited in mould steel matrix；Second stage cycle alternating deposit CrN/AlTiN on the basis of CrN tack coats Supporting layer；Phase III is passed through O simultaneously into furnace chamber2And N2And make to be passed through O2Flow linear rise, N2Flow linear decline, protects Hold the constant making AlTiON gradient layers of chamber pressure；Fourth stage keeps N2And O2The constant making AlTiON functional layers of flow；The The high-temp in-situ annealing in vacuum cavity of five stage CrN/AlTiN/AlTiON complex gradient layers.
Deposition parameter is as follows：
Step 1：The substrate for cleaning up is fixed on the carrier of coating chamber, the distance of target to substrate is 22cm, opens machine Tool pump and molecular pump evacuation make cavity background vacuum be less than 3 × 10-4Pa, opens heating system, is warming up to 450 °C, Opening carrier makes its 8 r/min rotational speed, and Ar gas 320SCCM are passed through into cavity room, and adjustment pressure in vacuum tank is 2 Pa, Substrate adds 800V back bias voltages, opens 2 pure Cr targets, and target current is 120A, the min of Glow Discharge Cleaning 20 is carried out to substrate; Adjustment negative bias is depressed into 200V, and 2 Cr target currents are adjusted to 90A, subsequently turn off Ar air valves while opening N2Throughput valve is to 350 SCCM, adjustment vacuum chamber pressure is the min of 3Pa deposition CrN tack coats 10；
Step 2：Depositing support layer CrN/AlTiN;
Adjustment N2To 450SCCM, 2 pure Cr target currents are adjusted to 110A to throughput, open 2 AlTi target currents and are adjusted to 115A, alternating deposit supporting layer CrN/AlTiN 60 min;
Step 3：Sedimentation gradient layer AlTiON；
O is passed through within the time period while into cavity2And N2Gas, keeps 2 AlTi target current 115A constant, cavity temperature control Make at 450 °C, as coating carries out N2Tolerance is from 450SCCM uniform descents to 410 SCCM, O2Flow is at the uniform velocity gone up from 0 SCCM It is raised to 35 SCCM, the min of depositing Al TiON gradient layer 25;
Step 4:Deposit functional layers AlTiON；
The stage continues to be passed through O to cavity2And N2Gas, is maintained at step 3 finishing phase N2And O2The constant i.e. N of throughput2Throughput For 410 SCCM, O2Throughput is 35SCCM, and 2 AlTi target currents are 115A, deposit functional layers AlTiON 30min;
Step 5：Complex gradient layer CrN/AlTiN/AlTiON high-temp in-situ annealing in vacuum cavity.
Turn off 2 AlTi target currents, turn off O2And N2Gas flow valve, chamber vacuum degree is adjusted to 4 × 10-3 Pa, substrate Temperature is heated to 850 °C, and insulation 5h makes multi-gradient film CrN/AlTiN/AlTiON high-temp in-situ annealing in vacuum cavity.
The detection sample of embodiment 1 ~ 3 obtains performance, as a result as shown in Table 1.
The properties of sample of one embodiment of table 1 ~ 3 is detected
As shown in Table 1, after testing embodiment 1, embodiment 2 and the sample of embodiment 3 its hardness are respectively 30.8Gpa, 31.2 Gpa With 33.7 Gpa；Film-substrate cohesion is respectively 77N, 95N and 84N；Highest oxidation resistance temperature be respectively 915 °C, 962 °C and 1036°C；In 1M H2SO4Three electrode test embodiments 1, embodiment 2 and the sample of embodiment 3 in solution, corrosion electric current density difference For 0.271 uA/cm2、0.158 uA/cm2With 0.204 uA/cm2, embodiment in testing result three embodiments shown above The sample of 2 depositions has highest film-substrate cohesion and corrosion resistance.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (2)

1. a kind of AlTiON hot die steels complex gradient coating, it is characterised in that between substrate surface and AlTiON functional layers Be sequentially depositing tack coat CrN, supporting layer CrN/AlTiN, gradient layer AlTiON, wherein supporting layer CrN/AlTiN by CrN, AlTiN alternating deposits make.
2. a kind of preparation method of AlTiON hot die steels complex gradient coating as claimed in claim 1, it is characterised in that The coating is prepared by ion arc PVD deposition, is comprised the following specific steps that：
Step 1：The substrate for cleaning up is fixed on the carrier of coating chamber, carrier rotating speed is controlled in 2 ~ 8 r/min, cavity temperature Degree control is passed through Ar 200 ~ 320SCCM of gas at 200 ~ 450 °C in cavity room, pressure in vacuum tank is 0.3 ~ 2 Pa, and substrate adds 600 ~ 800V back bias voltages, Cr target currents are controlled in 50 ~ 120A, and the min of Glow Discharge Cleaning 10 ~ 20 is carried out to substrate;Adjustment Negative bias added by substrate is depressed into 50 ~ 200V, and Cr target currents are adjusted to 50 ~ 90A, turns off Ar air valves while opening N2Throughput valve is extremely 250 ~ 350 SCCM, adjustment vacuum chamber pressure is the min of 1 ~ 3Pa deposition CrN tack coats 4 ~ 10；
Step 2：Adjustment N2To 380 ~ 450SCCM, Cr target currents are adjusted to 60 ~ 110A to throughput, and AlTi target currents are adjusted to 55 ~ 115A, alternating deposit supporting layer CrN/AlTiN 30 ~ 60 min;
Step 3：Cr target currents are closed, into cavity O is passed through2And N2Gas, keeps AlTi 55 ~ 115A of target current constant, cavity temperature Control at 200 ~ 450 °C, as coating carries out N2Throughput is from 380 ~ 450SCCM uniform descents to 340 ~ 410 SCCM, O2Gas Flow at the uniform velocity rises to 25 ~ 35 SCCM, the min of depositing Al TiON gradient layer 15 ~ 25 from 0 SCCM;
Step 4:Continue to be passed through O to cavity2And N2Gas, is maintained at step 3 finishing phase N2And O2Throughput is constant, AlTi targets electricity Flow constant, deposit functional layers 15 ~ 30min of AlTiON;
Step 5:Stop plated film, chamber vacuum degree is adjusted to 4 × 10-3 Pa, substrate temperature is heated to 650 ~ 850 °C, and insulation 3 ~ 5h high-temp in-situs are annealed.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108149194A (en) * 2018-01-26 2018-06-12 锐胜精机（深圳）有限公司 A kind of AlTiN coatings with structure gradient and preparation method thereof
CN110846618A (en) * 2019-11-11 2020-02-28 温州职业技术学院 High-entropy alloy composite coating for surface protection of aluminum die-casting mold
CN111826611A (en) * 2020-07-22 2020-10-27 常州夸克涂层科技有限公司 AlTiN gradient hard coating and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108149194A (en) * 2018-01-26 2018-06-12 锐胜精机（深圳）有限公司 A kind of AlTiN coatings with structure gradient and preparation method thereof
CN110846618A (en) * 2019-11-11 2020-02-28 温州职业技术学院 High-entropy alloy composite coating for surface protection of aluminum die-casting mold
CN110846618B (en) * 2019-11-11 2022-04-19 温州职业技术学院 High-entropy alloy composite coating for surface protection of aluminum die-casting mold
CN111826611A (en) * 2020-07-22 2020-10-27 常州夸克涂层科技有限公司 AlTiN gradient hard coating and preparation method thereof

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