CN104087898B - TiSiCN nanometer composite coating with ultrahigh hardness and low friction coefficient and preparation method of TiSiCN nanometer composite coating - Google Patents
TiSiCN nanometer composite coating with ultrahigh hardness and low friction coefficient and preparation method of TiSiCN nanometer composite coating Download PDFInfo
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- CN104087898B CN104087898B CN201410341995.8A CN201410341995A CN104087898B CN 104087898 B CN104087898 B CN 104087898B CN 201410341995 A CN201410341995 A CN 201410341995A CN 104087898 B CN104087898 B CN 104087898B
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Abstract
The invention discloses a TiSiCN nanometer composite coating with ultrahigh hardness and low friction coefficient and a preparation method of the TiSiCN nanometer composite coating. The TiSiCN nanometer composite coating with ultrahigh hardness and low friction coefficient is prepared by performing magnetron sputtering reaction deposition on a TiSiC composite target on a matrix subjected to polishing, ultrasonic cleaning and ion cleaning by adopting a multi-target magnetron sputtering instrument. In the TiSiC composite target, according to the atomic ratio, Ti accounts for 84 percent, and the total atomic weight of Si and C is 16 percent. The TiSiCN nanometer composite coating has the hardness of 36.1-46.0GPa and the friction coefficient of 0.30-0.38 between the composite coating and a GCr15 steel ball and can be used for dry and high-speed cutting tools and surfaces of parts serving under frictional wear conditions, so that the surface performances of the tools and parts are improved, and the service lives of the tools and parts are prolonged. The preparation method of the composite coating has the advantages of simple process, high deposition speed, low cost and high bonding strength.
Description
Technical field
It is more particularly to a kind of with ultrahigh hardness, low-friction coefficient the present invention relates to a kind of New Rigid protective coating
TiSiCN nano-composite coatings and preparation method thereof, carrying out further reinforcing using the nano combined membrane coats of C doping TiSiN is
Of the invention the characteristics of, simultaneously because the doping of C element makes coating have relatively low coefficient of friction.
Background technology
With the progress and the development of science and technology of society, material surface performance requirement more and more higher, high rigidity, wear-resisting, corrosion resistant
A variety of indexs such as corrosion, resistance to elevated temperatures are to weigh the important indicator of current cutting performance, are to meet higher and higher engineering need
Will, it is a kind of economical and practical effective way that improves material surface performance to coat one layer of hard coat in material surface, hard
Coating applies very wide, particularly in metal cutting as an important branch of mechanical function film in machine tools
Account for leading position.Hard coat can improve the surface property of material, reduce the friction and wear with workpiece, effectively improve material
Material case hardness, toughness, wearability and high-temperature stability, increase substantially the service life of coating product.Its development is adapted to
Modern manufacturing industry required the high-tech of metal cutting tool, causes the great change of cutter material and performance, extensively can should
For fields such as machine-building, auto industry, textile industry, geological drilling, mould industry, Aero-Space.
For many years, the nano combined membrane coats of TiSiN are due to high hardness, wearability, corrosion resistance, higher antioxidation
The advantages of performance, is widely used in protectiveness hard coating material.However, as current cutting technology is gradually to high-speed cutting
Develop with DRY CUTTING direction, the performance such as hardness, antioxygenic property, heat stability to coating material proposes higher wanting
Ask.Traditional TiSiN composite coatings can not gradually meet the requirement of modern cutting technology, therefore new in the urgent need to developing
Protective coating material.With the development of nanometer science and technology, the further research of nano-composite coating becomes hard coat
The important development direction of material.So-called nano combined membrane coat is a kind of superhard painting typically strengthened with nanostructured
Layer, the coating is mutually to wrap up the tridimensional network that matrix phase is formed by interface.Its hard mechanism of cause is mutually wrapped in its interface to be received
The composite construction of meter Jing is relevant, the nano combined membrane coat of preferable TiSiN by nano-scale TiN crystal grain and Si3N4Amorphous phase group
Conjunction is formed.Whole film layer is nanocrystalline based on TiN isometry, Si3N4The nanocrystalline surroundings of TiN are mutually wrapped in as interface.Due to
TiN nanometers are transgranular without dislocation, it is difficult to deform, and result from low intensive Si3N4Micro-crack in the phase of interface is then due to by TiN
Nanocrystalline stop and be difficult to extend so that the hardness of nano composite membrane is improved.Therefore, nano-composite coating is new guarantor
The important development direction of shield type hard coat.
Learnt by reading up the literature, the nano combined membrane coats of TiSiCN have successfully been obtained by various methods at present, obtained
Many beneficial achievements, such as plasma enhanced chemical vapor deposition TiSiCN nano composite membranes.By inquiry, retrieve as
Descend the Chinese patent about preparing the nano combined membrane coats of TiSiCN：
The patent of Application No. 201110047212.1 relate to a kind of medium frequency magnetron sputtering technology and prepare TiSiCN nanometers
The method of composite lubricating film.The present invention utilizes medium frequency magnetron sputtering technology, is combined by reacting gas sputtering TiSi of CH4 and N2
Target, by Ti and Si atomic ratios, CH4 and N2 gas ratios, pulsed bias in regulation composition target the nano combined profits of TiSiCN are prepared
Sliding coating.The present invention solves the limitation of single TiC, TiN and DLC film tribological property, overcomes CVD preparation
The big difficult problem of TiSiCN coating residual gas toxicity.The coating of preparation has higher hardness, low coefficient of friction and good
Wear resistence, it is adaptable to the self-lubricating abrasion-resistant thin film on the component of machine surface such as bearing, small-sized rotating shaft and space mechanical moving components.It is a kind of
TiSiN+ZrSiN composite Nano coated cutting tools and preparation method thereof, belong to machine cut manufacture field, using multi-arc ion coating+
Prepared by the method for medium frequency magnetron sputtering, its structure is multiple structure, and tool surface is ZrSiN layers, ZrSiN layers and TiSiN layers it
Between have TiZrSiN transition zones, have Ti transition zones between TiSiN layers and matrix, the atom of Si contents wherein in TiSiN and ZrSiN layers
Percentage ratio is 6～10%, and TiSiN applies floor height is rigid and ZrSiN coating low-friction coefficient good combinations in the patent, makes cutter
Not only there is high rigidity, also good friction and wear behavior and excellent high temperature oxidation resistance, can reduce in working angles viscous
Knot, reduces tool wear, improves cutter life.
The patent of Application No. 200880018340. relate to a kind of surface-coated cutting tool including base material and in the base
The film formed on material, it is characterised in that the film includes being combined super multilayer film, the compound super multilayer film be by one or
Multiple the first to surpass multilayer film and one or more the second surpass multilayer film and are alternately stacked and obtain, the above-mentioned multilayer film that the first surpasses is logical
Cross and one or more A1 layers and one or more B layers are alternately stacked and are formed, the above-mentioned multilayer film that the second surpasses is by by one
Individual or multiple A2 layers and one or more C layers are alternately stacked and are formed, above-mentioned A1 layers and each free TiN of above-mentioned A2 layers, TiCN,
Any one composition in TiAlN and TiAlCN, above-mentioned B layers are made up of TiSiN or TiSiCN, and above-mentioned C layers by AlCrN or
AlCrCN is constituted.
The patent of Application No. 201010510348.7 relate to a kind of hard coat, and the hard coat is multiple including one nanometer
Layer is closed, the nanometer composite layer includes some TiN layers and some SiCN layers, and the TiN layer and SiCN layers are arranged alternately.The present invention is also
A kind of covering member with the hard coat and the preparation method of the covering member are provided.The hard coating hardness of the present invention is high,
With preferable anti-wear performance and high-temperature oxidation resistance.
The patent of Application No. 201010192207.5 relate to a kind of CrTiAlSiN nano-composite coatings, deposition this
Cutter of coating and preparation method thereof.The composite coating includes tack coat, supporting layer and main wearing layer, and tack coat is Cr, supports
Layer is CrN, and main wearing layer is to be replaced the compound painting of the CrSiN/TiAlSiN nanometer multilayers for constituting with TiAlSiN layers by CrSiN layers
Layer, or the nc-CrTiAlN/a-Si of amorphous Si3N4 is embedded in by nanocrystalline CrTiAlN3N4Nanocrystalline composite coating.Will be above-mentioned viscous
Knot is deposited upon on tool matrix, and redeposited supporting layer and main wearing layer obtain depositing the cutter of the coating.Institute of the present invention
Obtain CrTiAlSiN nano-composite coatings and have the advantages that hardness is high, coefficient of friction is low, adhesive force is strong, deposition has the knife of the coating
Tool has high case hardness, stronger film-base adhesive force, good anti-wear performance and resistance to elevated temperatures.
The patent of Application No. 96110195.4 relate to one kind and be coated with single or multiple lift exotic material layer (wherein
Layer is by single-phase k-Al2O3Constitute) object, it is characterised in that crystal has preferential in the growth of (210) direction on coated objects surface
Microstructure.Coated cutting tool of the invention shows enhanced abrasion resistance properties when ball bearing steel is processed.
However, above-mentioned existing coating there are still the problem that hardness, crocking resistance and deposition efficiency cannot be taken into account,
Have the shortcomings that hardness, high temperature oxidation resistance, production efficiency can not meet the performance requirement of high-speed cutting and DRY CUTTING.
The content of the invention
The invention aims to overcome the deficiencies in the prior art, there is provided one kind has ultrahigh hardness, low-friction coefficient
TiSiCN nano-composite coatings.The new approaches that TiSiN nano-composite coatings are further strengthened are made by C doping.Its
Adulterated using C and cause the further alloying of interface phase of coating nano composite structure, increased the springform between phase in coating
Amount is poor, Alternating stress field in coating is strengthened, while the nanocrystalline TiN that crystallization interface phase SiN in coating is wrapped up with it
In coherent strengthening, sliding of the TiN nanocrystals along crystal boundary is hindered, it is suppressed that the microcosmic of TiSiCN nano composite membranes becomes
Shape, to reach the effect for improving consistency and elasticity modulus comprehensively, simultaneously because the doping of C element makes coating have relatively low friction
Coefficient.The coating can be used as the cutter coat of high-speed dry type cutting and the protective coating in other rub resistances abrasion fields.
An other purpose of the present invention is to provide a kind of above-mentioned TiSiCN nanometers with ultrahigh hardness, low-friction coefficient
The preparation method of composite coating, the preparation method has the advantages that production efficiency height, energy consumption are low, relatively low to equipment requirements.
Technical scheme
A kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient are to adopt multi-target magnetic control sputtering instrument,
Magnetron sputtering reactive deposition being carried out on matrix by TiSiC composite target materials and being formed, its thickness is preferably 2.5-4.0 μm；
Described matrix is metal, hard alloy, ceramics or single crystalline Si.
The above-mentioned preparation method with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient, specifically includes
Following steps：
（1）, cleaning matrix
First the matrix after polished process is sent into into ultrasonic washing unit, successively in analytically pure anhydrous alcohol and acetone
In utilize 15～30kHz ultrasound wave to carry out 5～10min of cleaning；Then carry out Ion Cleaning, will matrix put into vacuum chamber, take out
Vacuum is to 6 × 10-4Ar gas is passed through after Pa, maintains vacuum in 2-4Pa, the ion of 30min bangs when entering behavior to matrix with intermediate frequency
Hit（JGP-450 type magnetic control sputtering systems, Chinese Academy of Sciences Shenyang scientific instrument development center company limited）, power is 80-100W；
（2）, TiSiCN nano-composite coatings preparation
Matrix is inserted into multi-target magnetic control sputtering instrument and is rested on before TiSiC composition targets, by magnetron sputtering reactive deposition
Obtain and there is ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient；
The process control parameter of described magnetron sputtering reactive deposition process is：
In described TiSiC composite target materials, calculate by atomic ratio, wherein Ti is 16% for the total atom amount of 84%, Si and C,
Calculate by atomic ratio, wherein Si：C is 12%：4 %、2%：14 %、8 %：8%、4 %:12 % or 0 %：16 %；
A diameter of 75mm of TiSiC composite target materials；
Ar throughputs：30-50sccm, N2Throughput：4-10sccm；
Radio-frequency sputtering power 300W, time 2h；
Target-substrate distance 3-7cm；
Total gas pressure scope 0.2-0.4Pa；
Substrate temperature is 300 DEG C.
Above-mentioned gained with the crystallization interface phase in ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient
In coherent strengthening, there is the good column crystal of continuous, degree of crystallinity to the nanocrystalline TiN that SiN is wrapped up with it in coating.
The TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient of above-mentioned gained, its hardness is up to 36.1-
46.0GPa, is only 0.30-0.38 with the coefficient of friction of GCr15 steel balls, can be applicable to dry type, cutting tool for high speed cutting and
In the parts surface that fretting wear condition is on active service, so as to improve cutter and parts surface performance and used life.
The Advantageous Effects of the present invention
A kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient of the present invention, according to TiSiN nanometers
The deformation mechanism of composite membrane, when TiN crystallite dimensions are sufficiently small, during especially less than 10nm, dislocation motion no longer becomes material change
The micromechanism of shape, and material deformation depends primarily on sliding of the TiN nanocrystals along crystal boundary.The present invention is multiple in TiSiN nanometers
C element of adulterating in film is closed, is adulterated using C and the interface of coating is mutually complicated, increased the elastic modelling quantity between phase in coating
Difference, also causes Alternating stress field in coating to strengthen, while the nanocrystalline TiN that crystallization interface phase SiN in coating is wrapped up with it is in
Coherent strengthening, hinders sliding of the TiN nanocrystals along crystal boundary, therefore the microdeformation of suppression TiSiN nano composite membranes,
TiSiN nano composite membranes are made further to strengthen.Simultaneously because the doping of C element makes coating have relatively low coefficient of friction, therefore
A kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient of the present invention can be used as high speed, DRY CUTTING
Cutter coat and other rub resistances wear and tear the protective coating in fields.
Further, a kind of preparation with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient of the invention
Method, its preparation process has the advantages that production efficiency height, energy consumption are low, relatively low to equipment requirements, is suitable to large-scale production.
Description of the drawings
The constituency electricity with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient of Fig. 1, the gained of embodiment 2
Sub- diffraction pattern；
The transmission electricity with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient of Fig. 2, the gained of embodiment 2
Mirror figure；
Fig. 3 a, the gained of embodiment 2 with Si in ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient
XPS collection of illustrative plates；
The XPS with C in ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient of Fig. 3 b, the gained of embodiment 2
Collection of illustrative plates；
Fig. 3 c, the gained of embodiment 2 with Ti in ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient
XPS collection of illustrative plates；
The XPS with N in ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient of Fig. 3 d, the gained of embodiment 2
Collection of illustrative plates.
Specific embodiment
Below by specific embodiment and combine accompanying drawing the present invention is described in further detail, but be not intended to limit this
It is bright.
Preparation, sign and measuring instrument used by the present invention：
JGP-450 type magnetic control sputtering systems, Chinese Academy of Sciences Shenyang scientific instrument development center company limited；
D8 Advance type X-ray diffractometers, German Bruker companies；
NANO Indenter G200 type nano-hardness testers, Agilent Technologies of the U.S.；
HSR-2M coating friction wear testing machines, Ke Kaihua Science and Technology Development Co., Ltd.s in Lanzhou；
Tecnai G2 20 type high resolution transmission electron microscopies, FEI Co. of the U.S.；
Quanta FEG450 type scanning electron microscopes, FEI Co. of the U.S.；
Axis Ultra DLD type x-ray photoelectron spectroscopies, Britain Kratos.
Embodiment 1
A kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient, are to adopt multi-target magnetic control sputtering instrument,
Magnetron sputtering reactive deposition is carried out on matrix by TiSiC composite target materials and formed；
Described matrix is single crystalline Si.
The above-mentioned preparation method with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient, specifically includes
Following steps：
（1）, cleaning matrix
First the matrix after polished process is sent into into ultrasonic washing unit, successively in analytically pure anhydrous alcohol and acetone
In utilize 15～30kHz ultrasound wave to carry out 5～10min of cleaning；Then carry out Ion Cleaning, will matrix put into vacuum chamber, take out
Vacuum is to 6 × 10-4Ar gas is passed through after Pa, maintains vacuum in 2-4Pa, the ion of 30min bangs when entering behavior to matrix with intermediate frequency
Hit, power is 80-100W；
（2）, TiSiCN nano-composite coatings preparation
Matrix is inserted into multi-target magnetic control sputtering instrument and is rested on before TiSiC composition targets, by magnetron sputtering reactive deposition
Obtain and there is ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient；
The process control parameter of described magnetron sputtering reactive deposition process is：
In described TiSiC composite target materials, calculate by atomic ratio, wherein Ti is 16% for the total atom amount of 84%, Si and C,
Calculate by atomic ratio, wherein Si：C is 12%：4%；
A diameter of 75mm of TiSiC composite target materials；
Ar throughputs：38sccm, N2Throughput：5sccm；
Radio-frequency sputtering power 300W, time 2h；
Target-substrate distance 5cm；
Total gas pressure scope 0.4Pa；
Substrate temperature is 300 DEG C.
Using Quanta FEG450 type scanning electron microscope instruments, to above-mentioned gained with ultrahigh hardness, low friction
The thickness of the TiSiCN nano-composite coatings of coefficient is detected that its thickness is about 2.5um；
Using NANO Indenter G200 type nano-hardness tester instruments, to above-mentioned gained with ultrahigh hardness, low rub
The hardness for wiping the TiSiCN nano-composite coatings of coefficient is detected that its hardness is 36.1GPa；
Using HSR-2M coating friction wear testing machine instruments to above-mentioned gained with ultrahigh hardness, low-friction coefficient
TiSiCN nano-composite coatings are detected that it is with the coefficient of friction of GCr15 steel balls with the coefficient of friction of GCr15 steel balls
0.38。
Embodiment 2
A kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient, are to adopt multi-target magnetic control sputtering instrument,
Magnetron sputtering reactive deposition is carried out on matrix by TiSiC composite target materials and formed；
Described matrix is single crystalline Si.
The above-mentioned preparation method with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient, specifically includes
Following steps：
（1）, cleaning matrix
First the matrix after the polished process of one side is sent into into ultrasonic washing unit, successively in analytically pure anhydrous alcohol and
5～10min of cleaning is carried out in acetone using 15～30kHz ultrasound wave；Then Ion Cleaning is carried out, will matrix threading vacuum
Room, is evacuated down to 6 × 10-4Be passed through Ar gas after Pa, maintain vacuum in 2-4Pa, when entering behavior to matrix with intermediate frequency 30min from
Son bombardment, power is 80-100W；
（2）, TiSiCN nano-composite coatings preparation
Matrix is inserted into multi-target magnetic control sputtering instrument and is rested on before TiSiC composition targets, by magnetron sputtering reactive deposition
Obtain and there is ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient；
The process control parameter of described magnetron sputtering reactive deposition process is：
In described TiSiC composite target materials, calculate by atomic ratio, wherein Ti is 16% for the total atom amount of 84%, Si and C,
Calculate by atomic ratio, wherein Si：C is 8%：8%；
A diameter of 75mm of TiSiC composite target materials；
Ar throughputs：50sccm, N2Throughput：10sccm；
Radio-frequency sputtering power 300W, time 2h；
Target-substrate distance 5cm；
Total gas pressure scope 0.3Pa；
Substrate temperature is 300 DEG C.
Above-mentioned gained have ultrahigh hardness, low-friction coefficient TiSiCN nano-composite coatings after testing, its thickness is about
3.2um, hardness is 46.0GPa, is 0.35 with the coefficient of friction of GCr15 steel balls.
Using Tecnai G2 20 type high resolution transmission electron microscopies are to above-mentioned gained with ultrahigh hardness, low friction
The TiSiCN nano-composite coatings of coefficient are measured, and the SEAD figure of gained is as shown in figure 1, can from Fig. 1
Go out TiN（200）The ring of light becomes clear, and has been indicated above forming preferable column crystal in thin film, TiN diffraction maximums（200）Degree of crystallinity is preferable；
Using Tecnai G2 20 type high resolution transmission electron microscopies are to above-mentioned gained with ultrahigh hardness, low friction
The TiSiCN nano-composite coatings of coefficient are measured, and the transmission electron microscope picture of gained is as shown in Fig. 2 as can be seen from Figure 2 thin
Presence of an interface mutually wraps up the structure and continuous striped of crystal phase in film, has been indicated above thin film and there is crystallization interface mutually to wrap up
Nanocrystalline nano composite structure, while thin film also has the good column crystal of degree of crystallinity；
Using Axis Ultra DLD types x-ray photoelectron spectroscopies to above-mentioned gained with ultrahigh hardness, low friction
The TiSiCN nano-composite coatings of coefficient are measured, and the TiSiCN nanometers with ultrahigh hardness, low-friction coefficient of gained are answered
Close the XPS collection of illustrative plates of Si in coating as shown in Figure 3 a, it can be seen that Si2p valence links are the combining form of Si-N in thin film from Fig. 3 a,
It has been indicated above containing SiN phases in thin film；
Using Axis Ultra DLD types x-ray photoelectron spectroscopies to above-mentioned gained with ultrahigh hardness, low friction
The TiSiCN nano-composite coatings of coefficient are measured, and the TiSiCN nanometers with ultrahigh hardness, low-friction coefficient of gained are answered
Close the XPS collection of illustrative plates of C in coating as shown in Figure 3 b, it can be seen that C1s valence links are the combining form of C-C from Fig. 3 b, be indicated above
Contain C simple substance phases in thin film；
Using Axis Ultra DLD types x-ray photoelectron spectroscopies to above-mentioned gained with ultrahigh hardness, low friction
The TiSiCN nano-composite coatings of coefficient are measured, and the TiSiCN nanometers with ultrahigh hardness, low-friction coefficient of gained are answered
Close the XPS collection of illustrative plates of Ti in coating as shown in Figure 3 c, combining form of the Ti2p valence links for TiN is can be seen that from Fig. 3 c, thus table
Contain TiN phases in clear thin film；
Using Axis Ultra DLD types x-ray photoelectron spectroscopies to above-mentioned gained with ultrahigh hardness, low friction
The TiSiCN nano-composite coatings of coefficient are measured, and the TiSiCN nanometers with ultrahigh hardness, low-friction coefficient of gained are answered
Close the XPS collection of illustrative plates of N in coating as shown in Figure 3 d, it can be seen that N1s valence links are the combining form of TiN from Fig. 3 d, thus enter one
Step is indicated and contain in thin film TiN phases.
Embodiment 3
A kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient, are to adopt multi-target magnetic control sputtering instrument,
Magnetron sputtering reactive deposition is carried out on matrix by TiSiC composite target materials and formed；
Described matrix is single crystalline Si.
The above-mentioned preparation method with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient, specifically includes
Following steps：
（1）, cleaning matrix
First the matrix after the polished process of one side is sent into into ultrasonic washing unit, successively in analytically pure anhydrous alcohol and
5～10min of cleaning is carried out in acetone using 15～30kHz ultrasound wave；Then Ion Cleaning is carried out, will matrix threading vacuum
Room, is evacuated down to 6 × 10-4Be passed through Ar gas after Pa, maintain vacuum in 2-4Pa, when entering behavior to matrix with intermediate frequency 30min from
Son bombardment, power is 80-100W；
（2）, TiSiCN nano-composite coatings preparation
Matrix is inserted into multi-target magnetic control sputtering instrument and is rested on before TiSiC composition targets, by magnetron sputtering reactive deposition
Obtain and there is ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient；
The process control parameter of described magnetron sputtering reactive deposition process is：
In described TiSiC composite target materials, calculate by atomic ratio, wherein Ti is 16% for the total atom amount of 84%, Si and C,
Calculate by atomic ratio, wherein Si：C is 4%:12%；
A diameter of 75mm of TiSiC composite target materials；
Ar throughputs：30sccm, N2Throughput：5sccm；
Radio-frequency sputtering power 300W, time 2h；
Target-substrate distance 5cm；
Total gas pressure scope 0.2Pa；
Substrate temperature is 300 DEG C.
After testing, there is above-mentioned gained ultrahigh hardness, the thickness of the TiSiCN nano-composite coatings of low-friction coefficient to be about
3.5um, hardness is 41.3GPa, is 0.33 with the coefficient of friction of GCr15 steel balls.
Embodiment 4
A kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient, are to adopt multi-target magnetic control sputtering instrument,
Magnetron sputtering reactive deposition is carried out on matrix by TiSiC composite target materials and formed；
Described matrix is single crystalline Si.
The above-mentioned preparation method with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient, specifically includes
Following steps：
（1）, cleaning matrix
First the matrix Jing after single-sided polishing process is sent into into ultrasonic washing unit, successively in analytically pure anhydrous alcohol and
5～10min of cleaning is carried out in acetone using 15～30kHz ultrasound wave；Then Ion Cleaning is carried out, will matrix threading vacuum
Room, is evacuated down to 6 × 10-4Be passed through Ar gas after Pa, maintain vacuum in 2-4Pa, when entering behavior to matrix with intermediate frequency 30min from
Son bombardment, power is 80-100W；
（2）, TiSiCN nano-composite coatings preparation
Matrix is inserted into multi-target magnetic control sputtering instrument and is rested on before TiSiC composition targets, by magnetron sputtering reactive deposition
Obtain and there is ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient；
The process control parameter of described magnetron sputtering reactive deposition process is：
In described TiSiC composite target materials, calculate by atomic ratio, wherein Ti is 16% for the total atom amount of 84%, Si and C,
Calculate by atomic ratio, wherein Si：C is 2%：14%；
A diameter of 75mm of TiSiC composite target materials；
Ar throughputs：32 sccm, N2Throughput：4sccm；
Radio-frequency sputtering power 300W, time 2h；
Target-substrate distance 5cm；
The Pa of total gas pressure scope 0.3；
Substrate temperature is 300 DEG C.
After testing, there is above-mentioned gained ultrahigh hardness, the thickness of the TiSiCN nano-composite coatings of low-friction coefficient to be about
4.0um, hardness is 39.4GPa, is 0.32 with the coefficient of friction of GCr15 steel balls.
Embodiment 5
A kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient, are to adopt multi-target magnetic control sputtering instrument,
Magnetron sputtering reactive deposition is carried out on matrix by TiSiC composite target materials and formed；
Described matrix is single crystalline Si.
The above-mentioned preparation method with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient, specifically includes
Following steps：
（1）, cleaning matrix
First the matrix Jing after single-sided polishing process is sent into into ultrasonic washing unit, successively in analytically pure anhydrous alcohol and
5～10min of cleaning is carried out in acetone using 15～30kHz ultrasound wave；Then Ion Cleaning is carried out, will matrix threading vacuum
Room, is evacuated down to 6 × 10-4Be passed through Ar gas after Pa, maintain vacuum in 2-4Pa, when entering behavior to matrix with intermediate frequency 30min from
Son bombardment, power is 80-100W；
（2）, TiSiCN nano-composite coatings preparation
Matrix is inserted into multi-target magnetic control sputtering instrument and is rested on before TiSiC composition targets, by magnetron sputtering reactive deposition
Obtain and there is ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient；
The process control parameter of described magnetron sputtering reactive deposition process is：
In described TiSiC composite target materials, calculate by atomic ratio, wherein Ti is 16% for the total atom amount of 84%, Si and C,
Calculate by atomic ratio, wherein Si：C is 0%：16%；
A diameter of 75mm of TiSiC composite target materials；
Ar throughputs：40sccm, N2Throughput：8 sccm；
Radio-frequency sputtering power 300W, time 2h；
Target-substrate distance 5cm；
Total gas pressure scope 0.4Pa；
Substrate temperature is 300 DEG C.
After testing, there is above-mentioned gained ultrahigh hardness, the thickness of the TiSiCN nano-composite coatings of low-friction coefficient to be about
3.1um, hardness is 38.2GPa, is 0.30 with the coefficient of friction of GCr15 steel balls.
In sum, a kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient of the invention be by
Prepared by magnetically controlled sputter method, the thickness of the TiSiCN nano-composite coatings of gained is about 2.5-4.0um, and hardness is 36.1-
46.0GPa, the coefficient of friction with GCr15 steel balls is 0.30-0.38, and hardness reaches highest 46.0GPa at embodiment 2,
Also there is relatively low coefficient of friction at the example simultaneously, be 0.35, the TiSiCN nano-composite coatings of gained are at embodiment 5
Coefficient of friction is minimum, and only 0.3, it is indicated above that the TiSiCN nano-composite coatings obtained by the present invention have ultrahigh hardness, low rub
Wipe coefficient.
The above be only the present invention be preferable to carry out case, it should be noted that for the general technology people in the field
Member, on the premise of without departing from the inventive method, can also make a little supplement and improvement, and these supplement and improve and also should be regarded as this
The protection domain of invention.
Claims (5)
1. a kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient, it is characterised in that described with superelevation
Hardness, the TiSiCN nano-composite coatings of low-friction coefficient are using multi-target magnetic control sputtering instrument, by TiSiC composite target materials successively
Carry out magnetron sputtering reactive deposition and formed on matrix after polished, ultrasound wave cleaning, Ion Cleaning；
Described matrix is metal, hard alloy, ceramics or single crystalline Si；
In described TiSiC composite target materials, calculate by atomic ratio, wherein Ti is 16% for the total atom amount of 84%, Si and C；It is described
TiSiC composite target materials in, by atomic ratio calculate, wherein Si：C is 12%：4%、8%：8%、4%:12%、2%：14%；
A diameter of 75mm of described TiSiC composite target materials.
2. a kind of TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient as claimed in claim 1, its feature
It is described magnetron sputtering reactive deposition, the technology controlling and process of its process is as follows：
Ar throughputs：30-50sccm, N2Throughput：4-10sccm；
Radio-frequency sputtering power 300W, time 2h；
Target-substrate distance 3-7cm；
Total gas pressure scope 0.2-0.4Pa；
Substrate temperature is 300 DEG C.
3. there is as claimed in claim 2 ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient, it is characterised in that
The described TiSiCN nano-composite coatings thickness with ultrahigh hardness, low-friction coefficient is 2.5-4.0 μm.
4. there is as claimed in claim 2 ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient, it is characterised in that
It is described with crystallization interface phase SiN in ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient and its wrap up
Nanocrystalline TiN is in coherent strengthening, and the good column crystal of continuous, degree of crystallinity occurs in coating.
5. the preparation with ultrahigh hardness, the TiSiCN nano-composite coatings of low-friction coefficient as described in claim 1,2 or 3
Method, it is characterised in that specifically include following steps：
（1）, cleaning matrix
First the matrix after polished process is sent into into ultrasonic washing unit, successively the profit in analytically pure anhydrous alcohol and acetone
5～10min of cleaning is carried out with 15～30kHz ultrasound wave；
Then Ion Cleaning is carried out；
Described Ion Cleaning will matrix put into vacuum chamber, be evacuated down to 6 × 10-4Ar gas is passed through after Pa, maintains vacuum to exist
2-4Pa, the ion bom bardment of 30min when entering behavior to matrix with intermediate frequency, power is 80-100W；
（2）, TiSiCN nano-composite coatings preparation
Matrix is inserted into multi-target magnetic control sputtering instrument and is rested on before TiSiC composition targets, obtained by magnetron sputtering reactive deposition
TiSiCN nano-composite coatings with ultrahigh hardness, low-friction coefficient.
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| EP4292736A4 (en) * | 2022-01-25 | 2024-05-29 | Sumitomo Electric Industries, Ltd. | Cutting tool and method for manufacturing same |
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