CN108796432A - A kind of AlTiN coatings and preparation method thereof - Google Patents
A kind of AlTiN coatings and preparation method thereof Download PDFInfo
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- CN108796432A CN108796432A CN201811062286.0A CN201811062286A CN108796432A CN 108796432 A CN108796432 A CN 108796432A CN 201811062286 A CN201811062286 A CN 201811062286A CN 108796432 A CN108796432 A CN 108796432A
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- 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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- 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
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- 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
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- 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
- C23C14/025—Metallic sublayers
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- 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
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- 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
- C23C14/14—Metallic material, boron or silicon
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Abstract
This application discloses a kind of AlTiN coatings and preparation method thereof, AlTiN coatings are made of Cr bombardments implant layer, CrN transition zones and AlTiN surface functional layers, the binding force of the AlTiN coatings and matrix is sufficiently strong, is not likely to produce peeling phenomenon, friction coefficient at high temperature is smaller.The preparation method includes cleaning matrix process, etching procedure, it deposits Cr and bombards implant layer process, deposit CrN transition zone processes, depositing Al TiN surface functional layers process and cooling process, in three specific deposition procedures, using cathode pulse arc technology, by adjusting pulsed arc power supply output current maximum value, minimum value, duty ratio, frequency, so that more highdensity plasma can be generated during pulsed discharge, the AlTiN coatings prepared compared to conventional arc ion plating technique, AlTiN coatings manufactured in the present embodiment are obviously improved with Coating Surface Roughness, surface bulky grain quantity significantly reduces, film layer compactness is closer, the more low advantage of friction coefficient under film-substrate cohesion higher and high temperature.
Description
Technical field
The present invention relates to Cutting-Tool Coating Technology fields more particularly to a kind of AlTiN coatings and preparation method thereof.
Background technology
Cutter coat experienced great-leap-forward development from the 1970s, wherein using TiN as the first generation coating of representative
With higher hardness and wearability, tool sharpening efficiency and surface quality are significantly improved, is widely used.But TiN
Coating is just aoxidized when temperature is more than 600 DEG C, phenomena such as hardness decline, coating shedding occurs.Therefore, TiN coatings without
Method meets the requirement of modern machining.
Compared with TiN coatings, AlTiN coatings also have in addition to having the advantages that hardness is high, oxidizing temperature is up to other than 800 or more
There is the features such as film substrate bond strength is high, friction coefficient is small, thermal conductivity is low, is particularly suitable for high-speed cutting high-temperature alloy steel, stainless
The materials such as steel, titanium alloy, nickel-base alloy.In view of the advantage that AlTiN coatings are shown in terms of high-temperature behavior, it is expected to gradually
Substitute TiN coatings.
The AlTiN coatings that the prior art provides, including CrN transition zones and AlTiN surface functional layers.However, due to CrN mistakes
The atom percentage content for crossing each element in layer is undesirable, causes the binding force of AlTiN coatings and matrix insufficient, easy tos produce stripping
Fall phenomenon；The atom percentage content of each element is undesirable in AlTiN surface functional layers, leads to AlTiN coatings at high temperature
Friction coefficient is still larger.
The prior art additionally provides a kind of method preparing AlTiN coatings using arc ion plating (aip), because of arc ions
Plating has many advantages, such as that deposition rate height and film substrate bond strength are high, and this method has become the main method for preparing AlTiN coatings
One of.But this method is in deposition procedures, since arc ion plating output current is steady state value so that the plasma of generation
Volume density is not high enough, therefore leads to that the AlTiN coating surfaces of electric arc ion-plating deposition are coarse, bulky grain quantity is more, uses this
Friction coefficient is big at high temperature for AlTiN coatings prepared by method, is easier to wear.
Invention content
The purpose of the present invention is to provide a kind of AlTiN coatings and preparation method thereof, the combinations of the AlTiN coatings and matrix
Power is sufficiently strong, is not likely to produce peeling phenomenon, and friction coefficient at high temperature is smaller, and it is heavy which can solve the prior art
Long-pending AlTiN coating surfaces are coarse, bulky grain quantity is more, and friction coefficient is big under high temperature, is easier the problem of abrasion.
For this purpose, the present invention uses following technical scheme：
A kind of AlTiN coatings, including it is deposited on Cr bombardments implant layer, CrN transition zones and the AlTiN stacked gradually on matrix
Surface functional layer；
The atom percentage content of each element is in the CrN transition zones：Cr accounts for 40~70at%, and N accounts for 30~60at%；
The atom percentage content of each element is in the AlTiN surface functional layers：Al accounts for 20~40at%, and Ti accounts for 15~
35at%, N account for 30~60at%.
Optionally, the thickness of Cr bombardment implant layer is 0.2~0.8 μm, the thickness of the CrN transition zones is 0.5~
1.2 μm, the thickness of the AlTiN surface functional layers is 2~4 μm.
Optionally, described matrix is WC-Co hard alloy or high-speed steel.
A kind of preparation method preparing AlTiN coatings as described above, including cleaning matrix process, etching procedure and deposition work
Sequence, the deposition procedures include following process：
It deposits Cr and bombards implant layer process：Working bias voltage is adjusted to -80~-200V, 200 are passed through to vacuum chamber~
The Ar gas of 450sccm, lights Cr targets, adjusts the air pressure of the vacuum chamber to 0.8~3.0Pa, temperature to 350~500 DEG C, pulse
Arc power output current wave be rectangular wave, output current average current be 75~120A, frequency is 5~180Hz, duty
Than being 1%~70%, electric arc target electromagnetic coil output current is 0.5~6A, and deposition Cr bombards implant layer；
Deposit CrN transition zone processes：The working bias voltage is adjusted to -60~-150V, 250 are passed through to the vacuum chamber~
The N of 600sccm2Gas lights Cr targets, adjusts the air pressure of the vacuum chamber to 0.8~3.0Pa, temperature to 350~500 DEG C, described
Pulsed arc power supply output current wave be rectangular wave, output current average current be 75~120A, frequency be 5~180Hz,
Duty ratio is 1%~70%, and the electric arc target electromagnetic coil output current is 0.5~6A, deposits CrN transition zones；
Depositing Al TiN surface functional layer processes：The working bias voltage is adjusted to -50~-150V, is passed through to the vacuum chamber
The N of 250~600sccm2Gas lights AlTi targets, adjusts the air pressure of the vacuum chamber to 0.8~3.0Pa, temperature to 350~500
DEG C, the pulsed arc power supply output current wave be rectangular wave, output current average current be 70~110A, frequency 5
~180Hz, duty ratio are 1%~70%, and the electric arc target electromagnetic coil output current is 0.5~6A, depositing Al TiN surface works
Ergosphere.
Optionally, the cleaning matrix process includes：Described matrix is polished, it is polished clear to progress ultrasonic wave after minute surface
It washes, then air-dries and be put into the vacuum chamber.
Optionally, the ultrasonic cleaning is first to surpass with 10~20min of acetone ultrasonic cleaning described matrix, again with alcohol
Sound wave cleans described matrix 10~20min, described to air-dry to be dried up using nitrogen.
Optionally, the etching procedure includes：
The vacuum chamber is warming up to 300~500 DEG C, is 1.0*10 to the vacuum chamber to vacuum degree-3~
8.0*10-3Pa is passed through the Kr gas of the Ar gas and 50~250sccm of 100~400sccm to the vacuum chamber, adjusts working bias voltage
It is 20~300kHz to -500~-1000V, frequency, aura cleaning is carried out to described matrix surface, is passed through 100~400sccm's
The Kr gas of Ar gas and 50~250sccm, it is 15~35A to adjust the working bias voltage to -100~-300V, ion ource electric current, right
Described matrix carries out gas ion bombardment etching.
Optionally, further include after the deposition procedures：
Cooling process, the cooling process are to be passed through nitrogen cooling to the vacuum chamber after the deposition procedures terminate,
So that described matrix surface forms the AlTiN coatings.
Compared with prior art, the embodiment of the present invention has the advantages that：
An embodiment of the present invention provides a kind of AlTiN coatings and preparation method thereof, the binding forces of the AlTiN coatings and matrix
It is sufficiently strong, it is not likely to produce peeling phenomenon, and by adjusting the atom percentage content of each element in AlTiN surface functional layers, make
It is smaller to obtain the friction coefficient of AlTiN coatings at high temperature.The preparation method utilizes cathode pulse arc technology in deposition procedures,
By adjusting pulsed arc power supply output current maximum value, minimum value, duty ratio, frequency so that can during pulsed discharge
Generate more highdensity plasma, there is the AlTiN coatings prepared with this Coating Surface Roughness to be obviously improved, big of surface
Grain number amount significantly reduces, film layer compactness is closer, the more low advantage of friction coefficient under film-substrate cohesion higher and high temperature.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without having to pay creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is a kind of preparation method flow chart of AlTiN coatings provided in an embodiment of the present invention.
Fig. 2 is the oscillogram of pulsed arc power supply output current provided in an embodiment of the present invention.
Fig. 3 is the surface SEM figures for the AlTiN coatings that the prior art and the embodiment of the present invention are prepared respectively.
Fig. 4 is the XRD spectrum of AlTiN coatings provided in an embodiment of the present invention.
The AlTiN coatings that Fig. 5 is prepared for (400 DEG C and 600 DEG C) embodiment of the present invention under (25 DEG C) and high temperature at room temperature
Friction coefficient comparison diagram.
Fig. 6 is a kind of structural schematic diagram of AlTiN coatings provided in an embodiment of the present invention.
Specific implementation mode
In order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below in conjunction with the present invention
Attached drawing in embodiment, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that disclosed below
Embodiment be only a part of the embodiment of the present invention, and not all embodiment.Based on the embodiments of the present invention, this field
All other embodiment that those of ordinary skill is obtained without making creative work, belongs to protection of the present invention
Range.
Refering to Figure 1, present embodiments provide a kind of preparation method of AlTiN coatings, including carry out successively as
Lower process：Step S1 cleans matrix process；Step S2, etching procedure；Step S3, deposition Cr bombard implant layer process；Step
S4 deposits CrN transition zone processes；Step S5, depositing Al TiN surface functional layers process and step S6, cooling process.
It is polished to carrying out ultrasonic cleaning after minute surface specifically, the cleaning matrix process is to be polished to described matrix,
Then it air-dries and is put into vacuum chamber.Wherein, optionally, the ultrasonic cleaning be first use acetone ultrasonic cleaning described matrix 10~
20min, 10~20min of alcohol ultrasonic cleaning described matrix is used again.Optionally, described to air-dry to be dried up using nitrogen.
Further, the etching procedure is the vacuum chamber to be warming up to 300~500 DEG C, and take out to the vacuum chamber
Vacuum to vacuum degree is 1.0*10-3~8.0*10-3Pa, then to vacuum chamber be passed through 100~400sccm Ar gas and 50~
The Kr gas of 250sccm, and it is 20~300kHz to adjust working bias voltage to -500~-1000V, frequency, then to described matrix surface
Aura cleaning is carried out, is then passed through the Ar gas of 100~400sccm and the Kr gas of 50~250sccm again, then to adjust the work inclined
Be depressed into -100~-300V, ion ource electric current is 15~35A, gas ion bombardment etching finally is carried out to described matrix, when etching
Between be 15~45min.Wherein, it is to enable matrix to realize etching procedure to the adjusting of the temperature of vacuum chamber, pressure.Its
In, Ar gas and Kr gas are for aura cleaning and gas ion bombardment etching.
In etching procedure, working bias voltage is primarily to provide the energy of bombardment ion.Logical Ar gas and Kr gas, and it is inclined to work
Higher pressure is to improve the aura cleaning performance of gas ion bombardment matrix surface.
Further, the deposition Cr bombardments implant layer process is that the working bias voltage is adjusted to -80~-200V, Xiang Zhen
Empty room is passed through the Ar gas of 200~450sccm, lights Cr targets, then adjust the gas pressure in vacuum to 0.8~3.0Pa, temperature to
350~500 DEG C.Using cathode pulse arc technology, pulsed arc power supply output current wave be rectangular wave, output current it is flat
Equal electric current is 75~120A, frequency is 5~180Hz, duty ratio is 1%~70%.
Specifically, electric arc target electromagnetic coil output current is 0.5~6A, finally deposits Cr and bombard implant layer, the deposition
Cr bombards the implant layer time for 5~20min.
The maximum value and minimum value of pulsed arc power supply output current are adjustable therefore defeated by adjusting pulsed arc power supply
Go out maximum value, minimum value, duty ratio, the frequency of electric current so that more highdensity plasma can be generated during pulsed discharge
Body.Implant layer is bombarded with this adjusting control deposition Cr, is conducive to the deposition quality for promoting the deposition procedures.
Further, the deposition CrN transition zone processes are that the working bias voltage is adjusted to -60~-150V, to vacuum chamber
It is passed through the N of 250~600sccm2Gas, lights Cr targets, then adjusts the gas pressure in vacuum to 0.8~3.0Pa, temperature to 350
~500 DEG C.Using cathode pulse arc technology, pulsed arc power supply output current wave is that rectangular wave, output current are averaged
Electric current is 75~120A, frequency is 5~180Hz, duty ratio is 1%~70%.
Specifically, electric arc target electromagnetic coil output current is 0.5~6A, CrN transition zones, the deposition CrN are finally deposited
The time of transition zone is 15~40min.
The maximum value and minimum value of pulsed arc power supply output current are adjustable therefore defeated by adjusting pulsed arc power supply
Go out maximum value, minimum value, duty ratio, the frequency of electric current so that more highdensity plasma can be generated during pulsed discharge
Body.CrN transition zones are deposited with this adjusting control, are conducive to the deposition quality for promoting the deposition procedures.
Further, the depositing Al TiN surface functional layer processes are that the working bias voltage is adjusted to -50~-150V, to
Vacuum chamber is passed through the N of 250~600sccm2Gas, lights AlTi targets, then adjusts the gas pressure in vacuum to 0.8~3.0Pa, temperature
It is rectangular wave, output current that degree applies cathode pulse arc technology, pulsed arc power supply output current wave to 350~500 DEG C
Average current be 70~110A, frequency is 5~180Hz, duty ratio is 1%~70%.
Specifically, electric arc target electromagnetic coil output current is 0.5~6A, last depositing Al TiN surface functional layers are described heavy
The product AlTiN surface functional layer times are 100~180min.
The maximum value and minimum value of pulsed arc power supply output current are adjustable therefore defeated by adjusting pulsed arc power supply
Go out maximum value, minimum value, duty ratio, the frequency of electric current so that more highdensity plasma can be generated during pulsed discharge
Body.CrN transition zones are deposited with this adjusting control, are conducive to the deposition quality for promoting the deposition procedures.
In the specific deposition procedures of above three, that is, deposit Cr bombardment implant layers process, deposition CrN transition zones process, deposition
In AlTiN surface functional layer processes, the indoor temperature of vacuum, air pressure adjustment, be for meeting sedimentary condition.Deposition procedures
In, working bias voltage is primarily to provide the energy of bombardment ion.Relatively low working bias voltage is to reinforce metal ion and matrix
Combination.
In deposition procedures, changes the output current of electric arc target electromagnetic coil, electric arc target arcing surface spot Dispersed precipitate can be made,
Avoid target ablation.
CrN transition zones process is deposited primarily to improving with the binding force of matrix, the Cr in CrN transition zones and N element
Content is mainly realized by changing electric current and the nitrogen flow of electric arc target.
Finally, the cooling process is to be passed through nitrogen cooling to vacuum chamber after deposition procedures terminate so that described matrix
Surface forms the AlTiN coatings.Specifically, waiting for that the temperature of vacuum chamber is down to 70~100 DEG C, opens vacuum chamber and takes out matrix,
The coating formed at this time in matrix surface is AlTiN coatings.
It should be noted that voltage difference of the working bias voltage between grid bias power supply anode and matrix.In preparation process
In, matrix is with preset rotational speed, the step of uniformly to carry out each process to matrix.
The preparation method of AlTiN coatings provided in this embodiment, including cleaning matrix process, etching procedure, deposition Cr bang
Implant layer process, deposition CrN transition zones process, depositing Al TiN surface functional layers process and cooling process are hit, it is specific heavy at three
In product process, using cathode pulse arc technology, by adjusting pulsed arc power supply output current maximum value, minimum value, duty
Than, frequency so that more highdensity plasma can be generated during pulsed discharge.Compared to conventional arc ion plating technique system
Standby AlTiN coatings, AlTiN coatings manufactured in the present embodiment have Coating Surface Roughness be obviously improved, surface bulky grain number
Amount significantly reduces, film layer compactness is closer, the more low advantage of friction coefficient under film-substrate cohesion higher and high temperature.
Optionally, in another embodiment of the application, the specific preparation method of AlTiN coatings is as follows.By WC-Co hard
Alloy polishing treatment is cleaned by ultrasonic 15min respectively through acetone, alcohol, then is packed into vacuum chamber after being dried up with nitrogen.Open heating
Vacuum chamber is warming up to 350 DEG C by device, vacuum chamber to vacuum degree 3*10-3Pa or less.Be passed through 350sccm Ar gas and
The Kr gas of 100sccm, setting working bias voltage are equal to -1000V, and matrix rotating speed is 2.5r/min, frequency 150kHz, to matrix surface
Carry out aura cleaning, scavenging period 10min.Working bias voltage is down to -200V later, ion ource electric current 20A is set, uses ion
Source carries out gas ion bombardment etching, bombardment matrix 30min.Working bias voltage is adjusted to -100V again, is passed through the Ar gas of 400sccm,
The current average of pulsed arc power supply output current is set as 80A, duty ratio 30%, supply frequency 100Hz, adjusts vacuum
Room air pressure deposits Cr bombardment implant layers 15min to 1.5Pa.Working bias voltage is adjusted to -90V, Cr targets is lighted, is passed through 450sccm's
N2Gas sets current average 85A, duty ratio 30%, the supply frequency 100Hz of pulsed arc power supply output current, adjusts
Gas pressure in vacuum deposits CrN transition zones 35min to 1.5Pa.Finally it is passed through the N of 500sccm2Gas, working bias voltage are adjusted to -60V,
AlTi targets are opened, current average 85A, duty ratio 30%, the supply frequency 80Hz of pulsed arc power supply output current are set, are adjusted
Gas pressure in vacuum is saved to 2Pa, depositing Al TiN time 120min.It after the completion of plated film, waits for that vacuum room temperature is down to room temperature, opens true
Empty room takes out matrix.
Obtain after tested, Cr bombardments implant layer, CrN transition zones and AlTiN surface functional layers thickness be respectively 0.6 μm,
1.2 μm and 3.0 μm.The atom percentage content of each element is in CrN transition zones：Cr:70at%, N:30at%.The surfaces AlTiN
The atom percentage content of each element is in functional layer：Al:40at%, Ti:32at%, N:28at%.
The cathode pulse arc technology that the present embodiment uses, the waveform of pulsed arc power supply output current are as shown in Figure 2.
Pulse current waveform is rectangular wave, and in a cycle T, output current fluctuates between a minimum and a maximum value, and Ip is output
The difference of current maxima and minimum value.Duty ratio is that the time t of output current maximum value accounts for the percentage of cycle T, is equal to t/T.
Wherein frequency f=1/T.It is more rapid that effective current impulse can make arc spot run, and is avoided that arc spot stays in certain on target
Cause film surface particle excessive too long in one position.
Optionally, in another embodiment of the application, the specific preparation method of AlTiN coatings is as follows.By WC-Co hard
Alloy polishing treatment is cleaned by ultrasonic 10min respectively through acetone, alcohol, then is packed into vacuum chamber after being dried up with nitrogen.Open heating
Vacuum chamber is warming up to 300 DEG C by device, vacuum chamber to vacuum degree 5.0*10-3Pa.Be passed through 250sccm Ar gas and
The Kr gas of 150sccm, setting working bias voltage are -700V, matrix rotating speed 2r/min, frequency 120kHz, and brightness is carried out to matrix surface
Light cleans, scavenging period 10min.Working bias voltage is down to -200V later, ion ource electric current 30A is set, is carried out with ion source
Gas ion bombardment etches, bombardment matrix 35min.Working bias voltage is adjusted to -100V, is passed through the Ar gas of 300sccm, sets pulse
The current average of arc power output current be 70A, duty ratio 10%, supply frequency 50Hz, adjust gas pressure in vacuum to
1.2Pa, deposition Cr bombardment implant layers 10min.Working bias voltage is adjusted to -80V, lights Cr targets, is passed through the N of 350sccm2Gas, if
Current average 80A, duty ratio 20%, the supply frequency 70Hz of pulsed arc power supply output current, adjust gas pressure in vacuum to
1.5Pa, deposition CrN time 30min.Finally it is passed through the N of 500sccm2Gas, working bias voltage are set as -90V, open AlTi targets, setting
Current average 80A, duty ratio 20%, the supply frequency 75Hz of pulsed arc power supply output current, adjust gas pressure in vacuum to
1.8Pa, depositing Al TiN time 150min.It after the completion of plated film, waits for that vacuum room temperature is down to room temperature, opens vacuum chamber and take out matrix.
Obtain after tested, Cr bombardments implant layer, CrN transition zones and AlTiN surface functional layers thickness be respectively 0.4 μm,
0.8 μm and 3.2 μm.The atom percentage content of each element is in CrN transition zones：Cr:50at% and N:50at%.AlTiN tables
The atom percentage content of each element is in the functional layer of face：Al:36at%, Ti:15at%, N:49at%.
It please refers to shown in Fig. 3, (a), (b) two figure are by conventional arc ion plating and cathode pulse electric arc skill respectively in Fig. 3
The surface SEM figures of the AlTiN coatings of art deposition.Under identical amplification factor, it can be seen that cathode pulse arc technology deposition
AlTiN coating surface better quality, and surface bulky grain quantity is significantly reduced compared to conventional arc ion plating.
It please refers to shown in Fig. 4, Fig. 4 gives the XRD spectrum of AlTiN coatings.As can be drawn from Figure 4, as work is inclined
(111) peak of the increase of pressure, AlTiN solid solution phases gradually weakens, and (200) peak gradually increases, it is known that the preferred orientation of coating occurs
Variation.
Optionally, in another embodiment of the application, the specific preparation method of AlTiN coatings is as follows.By WC-Co hard
Alloy polishing treatment is cleaned by ultrasonic 15min respectively through acetone, alcohol, then is packed into vacuum chamber after being dried up with nitrogen.Open heating
Vacuum chamber is warming up to 350 DEG C by device, vacuum chamber to vacuum degree 3*10-3Pa or less.Be passed through 350sccm Ar gas and
Working bias voltage -800V, matrix rotating speed 2.5r/min, frequency 150kHz is arranged in the Kr gas of 100sccm, and brightness is carried out to matrix surface
Light cleans, scavenging period 10min.Working bias voltage is down to -150V later, ion ource electric current 15A is set, is carried out with ion source
Gas ion bombardment etches, bombardment matrix 30min.Working bias voltage is adjusted to -100V, is passed through the Ar gas of 400sccm, sets pulse
The current average of arc power output current be 85A, duty ratio 20%, supply frequency 100Hz, adjust gas pressure in vacuum to
1.8Pa, deposition Cr bombardment implant layers 10min.Working bias voltage is adjusted to -90V, lights Cr targets, is passed through the N of 450sccm2Gas, if
Determine current average 80A, duty ratio 30%, the supply frequency 100Hz of pulsed arc power supply output current, adjusts gas pressure in vacuum
To 1.8Pa, deposition CrN time 40min.Finally it is passed through the N of 500sccm2Gas, working bias voltage are set as -120V, open AlTi targets,
Current average 85A, duty ratio 30%, the supply frequency 100Hz of pulsed arc power supply output current are set, vacuum chamber gas is adjusted
It is depressed into 2Pa, depositing Al TiN time 150min.It after the completion of plated film, waits for that vacuum room temperature is down to room temperature, opens vacuum chamber and take out base
Body.
Can obtain after tested, Cr bombardments implant layer, CrN transition zones and AlTiN surface functional layers thickness be respectively 0.6 μm,
1.2 μm and 3.5 μm.The atom percentage content of each element is in CrN transition zones：Cr:70at%, N:30at%.The surfaces AlTiN
The atom percentage content of each element is in functional layer：Al:40at%, Ti:32at%, N:28at%.
Friction and wear behavior test is carried out to AlTiN coatings manufactured in the present embodiment.Friction test is in high temperature friction and wear
It is carried out on testing machine, using Al2O3Ball is used as to abrading-ball.Experiment linear velocity is set as 18cm/s, radius 2.0mm, and load is selected
5N.Coating carries out 8000 circle frictions at a temperature of each, and the friction coefficient of coating is provided in friction process by software is included.
Fig. 5 is the friction of (400 DEG C and 600 DEG C) AlTiN coatings manufactured in the present embodiment under (25 DEG C) and high temperature at room temperature
Index contrast figure.The average friction coefficient for the AlTiN coatings that under high temperature prepared by embodiment as can be seen from Figure 5 is than under room temperature
Low, therefore, AlTiN coatings manufactured in the present embodiment have the advantages that friction coefficient is low under high temperature really.
Optionally, in another embodiment of the application, the specific preparation method of AlTiN coatings is as follows.By WC-Co hard
Alloy polishing treatment is cleaned by ultrasonic 15min respectively through acetone, alcohol, then is packed into vacuum chamber after being dried up with nitrogen.Open heating
Vacuum chamber is warming up to 450 DEG C by device, vacuum chamber to vacuum degree 2*10-3Pa or less.Be passed through 200sccm Ar gas and
The Kr gas of 250sccm, setting working bias voltage are -900V, and matrix rotating speed is 3r/min, frequency 300kHz, is carried out to matrix surface
Aura cleans, scavenging period 12min.Working bias voltage is down to -100V later, sets ion ource electric current 25A, with ion source into
Row gas ion bombardment etches, bombardment matrix 30min.Working bias voltage is adjusted to -120V, is passed through the Ar gas of 400sccm, sets arteries and veins
Rush arc power output current current average be 90A, duty ratio 40%, supply frequency 110Hz, adjust gas pressure in vacuum to
2Pa, deposition Cr bombardment implant layers 25min.Working bias voltage is adjusted to -100V, lights Cr targets, is passed through the N of 450sccm2Gas, setting
Current average 90A, duty ratio 40%, the supply frequency 110Hz of pulsed arc power supply output current, adjust gas pressure in vacuum to
2Pa, deposition CrN time 40min.Finally it is passed through the N of 500sccm2Gas, working bias voltage are set as -90V, open AlTi targets, set arteries and veins
Rush current average 90A, duty ratio 40%, the supply frequency 120Hz of arc power output current, adjust gas pressure in vacuum to
1.8Pa, depositing Al TiN time 120min.It after the completion of plated film, waits for that vacuum room temperature is down to room temperature, opens vacuum chamber and take out matrix.
Obtain after tested, Cr bombardments implant layer, CrN transition zones and AlTiN surface functional layers thickness be respectively 0.5 μm,
0.8 μm and 3.0 μm.The atom percentage content of each element is in CrN transition zones：Cr:40at%, N:60at%.The surfaces AlTiN
The atom percentage content of each element is in functional layer：Al:28at%, Ti:21at%, N:51at%.
It please refers to shown in Fig. 6, present embodiments provides a kind of AlTiN coatings, preparation method system as described above may be used
It is standby to form.Specifically, the AlTiN coatings include Cr bombardments implant layer 11,12 and of CrN transition zones stacked gradually on matrix 10
AlTiN surface functional layers 13；The atom percentage content of each element is that Cr accounts for 40~70at%, N in the CrN transition zones 12
Account for 30~60at%；The atom percentage content of each element is that Al accounts for 20~40at% in the AlTiN surface functional layers 13,
Ti accounts for 15~35at%, and N accounts for 30~60at%.
Compared with prior art, the binding force of AlTiN coatings provided in this embodiment and matrix 10 is sufficiently strong, is not likely to produce
Peeling phenomenon, surface roughness are obviously improved, and by adjusting the atomic percent of each element in AlTiN surface functional layers 13
Content so that the friction coefficient of AlTiN coatings at high temperature is smaller.
Further, the thickness of the Cr bombardments implant layer 11 is 0.2~0.8 μm, and the thickness of the CrN transition zones 12 is
0.5~1.2 μm, the thickness of the AlTiN surface functional layers 13 is 2~4 μm.
Further, described matrix 10 is WC-Co hard alloy or high-speed steel.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to before
Stating embodiment, invention is explained in detail, it will be understood by those of ordinary skill in the art that：It still can be to preceding
The technical solution recorded in each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
Modification or replacement, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (8)
1. a kind of AlTiN coatings, which is characterized in that including being deposited on the Cr stacked gradually on matrix bombardments implant layer, CrN transition
Layer and AlTiN surface functional layers；
The atom percentage content of each element is in the CrN transition zones：Cr accounts for 40~70at%, and N accounts for 30~60at%；
The atom percentage content of each element is in the AlTiN surface functional layers：Al accounts for 20~40at%, and Ti accounts for 15~
35at%, N account for 30~60at%.
2. AlTiN coatings according to claim 1, which is characterized in that the thickness of Cr bombardment implant layer is 0.2~
0.8 μm, the thickness of the CrN transition zones is 0.5~1.2 μm, and the thickness of the AlTiN surface functional layers is 2~4 μm.
3. AlTiN coatings according to claim 1, which is characterized in that described matrix is WC-Co hard alloy or high speed
Steel.
4. a kind of preparation method preparing the AlTiN coatings as described in any one of claims 1 to 3, including cleaning matrix work
Sequence, etching procedure and deposition procedures, which is characterized in that the deposition procedures include following process：
It deposits Cr and bombards implant layer process：Working bias voltage is adjusted to -80~-200V, is passed through 200~450sccm's to vacuum chamber
Ar gas lights Cr targets, adjusts the air pressure of the vacuum chamber to 0.8~3.0Pa, temperature to 350~500 DEG C, pulsed arc power supply
Output current wave be rectangular wave, output current average current be 75~120A, frequency is 5~180Hz, duty ratio 1%
~70%, electric arc target electromagnetic coil output current is 0.5~6A, and deposition Cr bombards implant layer；
Deposit CrN transition zone processes：The working bias voltage is adjusted to -60~-150V, 250 are passed through to the vacuum chamber~
The N of 600sccm2Gas lights Cr targets, adjusts the air pressure of the vacuum chamber to 0.8~3.0Pa, temperature to 350~500 DEG C, described
Pulsed arc power supply output current wave be rectangular wave, output current average current be 75~120A, frequency be 5~180Hz,
Duty ratio is 1%~70%, and the electric arc target electromagnetic coil output current is 0.5~6A, deposits CrN transition zones；
Depositing Al TiN surface functional layer processes：The working bias voltage is adjusted to -50~-150V, 250 are passed through to the vacuum chamber
The N of~600sccm2Gas lights AlTi targets, adjusts the air pressure of the vacuum chamber to 0.8~3.0Pa, temperature to 350~500 DEG C,
The pulsed arc power supply output current wave be rectangular wave, output current average current be 70~110A, frequency be 5~
180Hz, duty ratio are 1%~70%, and the electric arc target electromagnetic coil output current is 0.5~6A, depositing Al TiN functions of surface
Layer.
5. preparation method according to claim 4, which is characterized in that the cleaning matrix process includes：To described matrix
Polishing, it is polished to ultrasonic cleaning is carried out after minute surface, it then air-dries and is put into the vacuum chamber.
6. preparation method according to claim 5, which is characterized in that the ultrasonic cleaning is first to use acetone ultrasonic wave clear
Wash 10~20min of described matrix, again with 10~20min of alcohol ultrasonic cleaning described matrix, it is described to air-dry to be blown using nitrogen
It is dry.
7. preparation method according to claim 4, which is characterized in that the etching procedure includes：
The vacuum chamber is warming up to 300~500 DEG C, is 1.0*10 to the vacuum chamber to vacuum degree-3~8.0*10- 3Pa is passed through the Kr gas of the Ar gas and 50~250sccm of 100~400sccm to the vacuum chamber, adjusts working bias voltage to -500
~-1000V, frequency be 20~300kHz, to described matrix surface carry out aura cleaning, be passed through 100~400sccm Ar gas and
The Kr gas of 50~250sccm, it is 15~35A to adjust the working bias voltage to -100~-300V, ion ource electric current, to the base
Body carries out gas ion bombardment etching.
8. preparation method according to claim 4, which is characterized in that further include after the deposition procedures：
Cooling process, the cooling process are to be passed through nitrogen cooling to the vacuum chamber after the deposition procedures terminate so that
Described matrix surface forms the AlTiN coatings.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109666887A (en) * | 2018-12-28 | 2019-04-23 | 广东工业大学 | A kind of TiAlN hard coat and its preparation method and application |
| CN109797365A (en) * | 2018-12-26 | 2019-05-24 | 广东工业大学 | A kind of TiAlN cutter coat and preparation method thereof and the cutting process cut using the cutter |
| CN110872697A (en) * | 2019-12-16 | 2020-03-10 | 广东正德材料表面科技有限公司 | Method for improving performance of multi-arc ion plating coating by Cr ion bombardment |
| 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 |
| CN112813389A (en) * | 2019-11-18 | 2021-05-18 | 河北召飞科技服务有限公司 | Method for reducing large liquid drops in multi-arc ion plating process |
| CN114164405A (en) * | 2021-12-07 | 2022-03-11 | 四川真锐晶甲科技有限公司 | Cutter thick film nitride coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103898445A (en) * | 2014-04-18 | 2014-07-02 | 常州多晶涂层科技有限公司 | Multilayer AlCrN cutting tool coating and preparation method thereof |
| CN104928638A (en) * | 2015-05-21 | 2015-09-23 | 广东工业大学 | AlCrSiN-based multilayer nanometer composite cutter coating layer and preparation method thereof |
| CN105088127A (en) * | 2015-08-31 | 2015-11-25 | 科汇纳米技术（深圳）有限公司 | Coating and preparing method thereof |
| CN108456843A (en) * | 2018-01-19 | 2018-08-28 | 广东工业大学 | A kind of high performance Ti AlSiN nano-composite coatings and its preparation method and application |
-
2018
- 2018-09-12 CN CN201811062286.0A patent/CN108796432A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103898445A (en) * | 2014-04-18 | 2014-07-02 | 常州多晶涂层科技有限公司 | Multilayer AlCrN cutting tool coating and preparation method thereof |
| CN104928638A (en) * | 2015-05-21 | 2015-09-23 | 广东工业大学 | AlCrSiN-based multilayer nanometer composite cutter coating layer and preparation method thereof |
| CN105088127A (en) * | 2015-08-31 | 2015-11-25 | 科汇纳米技术（深圳）有限公司 | Coating and preparing method thereof |
| CN108456843A (en) * | 2018-01-19 | 2018-08-28 | 广东工业大学 | A kind of high performance Ti AlSiN nano-composite coatings and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 傅玉灿主编: "《难加工材料高效加工技术》", 31 March 2016 * |
| 周书助主编: "《硬质材料与工具》", 31 August 2015 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109797365A (en) * | 2018-12-26 | 2019-05-24 | 广东工业大学 | A kind of TiAlN cutter coat and preparation method thereof and the cutting process cut using the cutter |
| CN109666887A (en) * | 2018-12-28 | 2019-04-23 | 广东工业大学 | A kind of TiAlN hard coat and its preparation method and application |
| CN112813389A (en) * | 2019-11-18 | 2021-05-18 | 河北召飞科技服务有限公司 | Method for reducing large liquid drops in multi-arc ion plating process |
| CN110872697A (en) * | 2019-12-16 | 2020-03-10 | 广东正德材料表面科技有限公司 | Method for improving performance of multi-arc ion plating coating by Cr ion bombardment |
| 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 |
| CN114164405A (en) * | 2021-12-07 | 2022-03-11 | 四川真锐晶甲科技有限公司 | Cutter thick film nitride coating and preparation method thereof |
| CN114164405B (en) * | 2021-12-07 | 2023-12-29 | 四川真锐晶甲科技有限公司 | Tool thick film nitride coating and preparation method thereof |
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Application publication date: 20181113 |