CN106544631A - A kind of chromium carbide multi-gradient composite coating of matrix surface and preparation method thereof - Google Patents
A kind of chromium carbide multi-gradient composite coating of matrix surface and preparation method thereof Download PDFInfo
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- CN106544631A CN106544631A CN201610939472.2A CN201610939472A CN106544631A CN 106544631 A CN106544631 A CN 106544631A CN 201610939472 A CN201610939472 A CN 201610939472A CN 106544631 A CN106544631 A CN 106544631A
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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
- C23C14/22—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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- 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
- C23C14/0635—Carbides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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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
- C23C14/0664—Carbonitrides
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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
- C23C14/14—Metallic material, boron or silicon
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Abstract
The present invention provides a kind of chromium carbide multi-gradient composite coating of matrix surface.The composite coating stacks gradually Cr layers, CrN layers, CrCN layers and CrC layers upwards from matrix surface.Compared with existing monolayer CrC coatings, the multilayered and graded structure can alleviate the diversity of composition, structure and physical property between coating and matrix, reduce coating stress, significantly improve the friction and wear behavior of coating.The present invention also provides one kind and adopts multi sphere ion plating technology, and with metal Cr as target, high-purity Ar is working gas, C2H2And N2For the method that reacting gas prepares the chromium carbide multi-gradient composite coating, the composition and structure of each layer is can control by adjusting the flow of various gases.
Description
Technical field
The present invention relates to the chromium carbide coating of matrix surface, more particularly to a kind of chromium carbide multi-gradient of matrix surface is again
Close coating and preparation method thereof.
Background technology
The nitride or carbide coating of transition metal is referred to as hard coat, and this type coating has higher hardness and good
Good chemical stability, is respectively provided with preferable wear-resisting and decay resistance under the specific conditions such as high temperature, high speed and high pressure, wide
It is general to be applied in the middle of commercial production.
The common preparation method of hard coat includes magnetron sputtering, multi-arc ion coating etc., prepared by wherein multi-arc ion coating
Hard coating hardness is higher, compactness is good, chemical stability is high, but during coatings growth often with drop, micropore,
The formation of the defects such as intercrystalline voids.These defects form fatigue statistic under the alternate stress effect that frrction load is produced, micro-
Crackle further spreads, crosses, and ultimately results in coating from matrix spalling failure.Further, since composition, group between coating and matrix
The difference with structure is knitted, the interface that there is a performance mutation, especially thermal coefficient of expansion differ greatly, it is difficult to reach enough
Bond strength.Under the conditions of the hertz stress that frrction load is produced, the residual stress produced in adding coating deposition process, film base
Interface becomes weak link, easily causes the stripping of coating and comes off, and affects the performance of coating performance.
Chromium carbide (CrC) plays important work in fields such as cutter, mould, blades as common hard coating material
With.But CrC toughness itself is poor, and the residual stress that PVD is produced in coating preparation process further can increase
The fragility of coating, under high contact stress Circulation, often there is brittle fracture and even peel off in CrC coatings.
At present, by multilayered and graded structure design release CrC coating internal stress, the research for improving coating toughness rarely has report
Road.And this multilayered and graded structure can improve blocking effect of the CrC coatings to corrosive medium, improve which in corrosive medium
Wear and corrosion behavior, with important using value.
The content of the invention
For the above-mentioned state of the art, the technical purpose of the present invention is to design a kind of CrC composite coatings of matrix surface, the painting
Layer has high bond strength with matrix, and with the excellent combination property such as high rigidity, low wear rate, high corrosion-resistant.
In order to realize above-mentioned technical purpose, the present inventor designs middle composite layer between matrix and CrC coatings：Cr layers,
CrN layers and CrCN layers, i.e. stack gradually Cr layers, CrN layers, CrCN layers, CrC layers upwards from matrix surface.In the application, should
CrC composite coatings are referred to as CrC multi-gradient composite coatings.
Preferably, in CrC layers, along stacked direction, C element content gradually increases.
Preferably, in CrCN layers, along stacked direction, C element content gradually increases.
Preferably, in CrN layers, along stacked direction, N element content gradually increases.
Preferably, described Cr thickness degree is 100nm～500nm.
Preferably, described CrN thickness degree is 100nm～500nm.
Preferably, described CrCN thickness degree is 100nm～1 μm.
Preferably, described CrC thickness degree is 1 μm～10 μm.
Compared with the CrC layers of existing matrix surface, above-mentioned CrC multi-gradients composite coating has the advantages that：
(1) multiple intermediate layers are designed in composite coating and can forms gradient transition structure, the structure can effectively alleviate top
The diversity of composition, structure and physical property between layer CrC layers and matrix, so as to reducing internal stress and improving coating and matrix
Bond strength.Also, multiple solutions between layers can destroy the columnar growth structure of coating, block along column crystal crystal boundary
Reach the penetrability passage of matrix such that it is able to effectively intercept infiltration of the corrosive medium to coating, improve the media-resistant of CrC coatings
Corrosive nature.In addition, hard CrC layers are located at top, with low wear rate, low-friction coefficient.
(2) in composite coating, stoichiometric proportion of the element ratio of C and Cr more than CrC in the CrC layers of preferred top,
Excessive C is present with a-C phases form, makes coating be in CrC/a-C Two-phase composite structures.In this configuration, a-C phases can be effective
Filling CrC crystal boundaries, so as to be conducive to the compactness of coating, can further improve the hardness and wear resistance of coating, and its hardness can
Up to more than 30GPa, wear rate is up to 10-16m3/ Nm magnitudes.Further preferably, along stacked direction in the CrC layers of top
(direction i.e. from bottom to top), C element content gradually increases, and at this moment in CrC layers, floor portions are based on hard phase CrC, non-
Brilliant carbon content is less, coating can be made to have good bearing capacity, and surface part to lubricate based on phase a-C phase, in a-C
sp2C-C is sheet graphite-structure, with low shear stress, easily forms a-C transfers on antithesis surface in friction process
Film such that it is able to effectively reduce the coefficient of friction of composite coating so as to which the average friction coefficient in atmospheric environment can be as little as
Less than 0.2.
(3) composite coating has good decay resistance in corrosive medium (such as sea water etc.), in high speed, height
Under load, corrosive environment, the matrix of operation has good protective action, such as tool for cutting machining and briny environment machinery
Motion parts etc. (such as piston ring, gear, valve, slide plate, sealing ring etc.), can effectively improve the combination property and clothes of matrix
The labour life-span, with good using value.
Present invention also offers a kind of method for preparing above-mentioned CrC multi-gradients composite coating, using multi-arc ion coating skill
Art, the matrix after surface cleaning processing is placed in filming equipment vacuum cavity, with metal Cr as target, with high-purity Ar as work
Gas, with C2H2And N2For reacting gas, back bias voltage is applied to matrix, target current is applied to Cr targets, CrC is deposited in matrix surface
Multi-gradient composite coating, specific implementation step are as follows：
Step 1, Ar gases are passed through, Cr layers are deposited in matrix surface；
Preferably, Ar flows are maintained at 200sccm～400sccm；
Preferably, Cr target currents be 40～80A, substrate negative voltage be -20～-50V, sedimentation time 10min～
30min；
Preferably, heating-up temperature is 400 DEG C～450 DEG C；
Step 2, continue to be passed through Ar gases, and be passed through N2, CrN layers are deposited in Cr layer surfaces；
Preferably, Ar gas flows are gradually decreased, N2Gas flow gradually increases.Further preferably, Ar gases are initial
Flow is 200sccm～400sccm, and termination flow is 0sccm；N2Gas initial flow is 0sccm, terminates flow and is
350sccm～800sccm；It is highly preferred that in deposition process, Ar gas flows are uniformly reduced, N2Gas flow uniformly increases.
Preferably, Cr target currents be 40～80A, substrate negative voltage be -20～-50V, sedimentation time 10min～
60min；
Step 3, stopping are passed through Ar gases, continue to be passed through N2, and it is passed through C2H2, CrCN layers are deposited in Cr layer surfaces；
Preferably, Cr target currents be 40～80A, substrate negative voltage be -20～-100V, sedimentation time 10min～
60min；
Preferably, N2Gas flow is 350sccm～800sccm；
Preferably, C2H2Gas flow gradually increases.Further preferably, in deposition process, C2H2Gas initial flow
For 0sccm, termination flow is 30sccm～100sccm.It is highly preferred that in deposition process, C2H2Gas flow uniformly increases.
Step 4, stopping are passed through N2, continue to be passed through C2H2, and Ar is passed through, CrC layers are deposited in CrCN layer surfaces；Also,
In deposition process, C2H2Gas flow gradually increases.
Preferably, Cr target currents are 40～80A, substrate negative voltage is -50～-300V, sedimentation time 1h～3h；
Preferably, Ar flows are maintained at 200sccm～400sccm.
Preferably, C2H2Initial flow is 50sccm～100sccm, and termination flow is 100sccm～200sccm；Enter one
Step is preferred, in deposition process, C2H2Gas flow uniformly increases.
Described Cr target numbers are not limited, preferably, in 2≤Cr target number≤8, and centered on matrix, Cr targets are excellent
Elect symmetrical as.
Preferably, described Cr targets purity is more than 99%.
Preferably, described C2H2、N2And Ar purity selects more than 99.9%.
Preferably, after CrC multi-gradients composite coating deposition is finished, less than 220 are cooled in vacuum environment, so
Less than 100 DEG C are cooled in nitrogen protection atmosphere afterwards, deflation begins to speak to come out of the stove, i.e., CrC multi-gradients are obtained in matrix surface multiple
Close coating.
The cleaning treatment of described matrix surface include be cleaned by ultrasonic, multi-arc ion coating reverse sputtering cleaning etc. in one kind or
It is several.Wherein, the cleaning of multi-arc ion coating reverse sputtering is referred to and for matrix to be put into multi-arc ion plating equipment cavity, and cavity is passed through high-purity
Ar, with metal Cr as target, applies DC current to Cr targets, and the bias reverse sputtering that bombardment matrix is carried out under substrate negative voltage is clear
Wash.
Preferably, described cavity temperature is 300～400 DEG C.
Preferably, the front cavity base vacuum of cleaning is evacuated to 3 × 10-3Pa～5 × 10-3Pa。
Preferably, described Ar flows are 100～300sccm.
Preferably, described target current is 50～70A.
Preferably, described substrate negative voltage is -800～-1300V.
Above-mentioned preparation method adopts multi sphere ion plating technology, by adjust the flow of various gases can control each layer into
Divide and structure, have the advantages that：
(1) it is simple, be passed through by control gas just Cr layers, CrN layers, CrCN can be stacked gradually upwards in matrix surface
Layer, CrC layers.
(2) in the deposition process of composite coating top CrC layer, gradually increase C2H2Flow the C in coating can be made first
Gradient increases element from bottom to top.When in coating, C/Cr ratios are more than CrC stoichiometric proportions, excessive C can be deposited with a-C phase forms
Coating is made to be in CrC/a-C Two-phase composite structures.And a-C phases can effectively fill CrC crystal boundaries, CrC preferential growths are hindered, broken
Bad its columnar crystal structure, so as to form the coating structure of densification, is conducive to improving coating hardness and wearability.Additionally, CrC layers bottom
, based on hard phase CrC, amorphous carbon content is less for layer segment, and this can ensure that coating has good bearing capacity；And CrC layers
Surface part to lubricate based on phase a-C phase, the sp in a-C2C-C is sheet graphite-structure, with low shear stress, is being rubbed
Easily a-C transfer membranes are formed on antithesis surface during wiping, so as to effectively reduce the coefficient of friction of composite coating.
(3) there are multiple intermediate layers in composite coating, gradient transition structure can be formed, the structure can effectively alleviate top
The diversity of composition, structure and physical property between layer CrC layers and matrix, so as to reducing internal stress and improving coating and matrix
Bond strength.Also, multiple solutions between layers can destroy the columnar growth structure of coating, block along column crystal crystal boundary
The penetrability passage of matrix is reached, the media-resistant corrosion of CrC coatings so as to effectively intercept infiltration of the corrosive medium to coating, is improved
Performance.In addition, when depositing inter-layer CrN layers, CrCN layers, C element in coating, N element can be made by adjusting gas flow
Gradient transition structure is formed, the structure can effectively alleviate composition between top layer CrC layers and matrix, structure and physical property
Diversity, so as to further reducing internal stress and improving the bond strength of coating and matrix.
(3) experimental verification, may be up to more than 30GPa using the hardness of composite coating obtained in the method, and wear rate is up to 10-16m3/ Nm magnitudes.Additionally, average friction coefficient in atmospheric environment can as little as less than 0.2.
Description of the drawings
Fig. 1 is the structural representation of the CrC multi-gradient composite coatings in the embodiment of the present invention 1 based on 316 rustless steels
Figure；
Fig. 2 is the scanning in the CrC multi-gradient composite coatings section in the embodiment of the present invention 1 based on 316 rustless steels
Electronic Speculum result figure；
Fig. 3 is the glow discharge of the CrC multi-gradient composite coatings in the embodiment of the present invention 1 based on 316 rustless steels
Spectral results figure；
Fig. 4 is CrC multi-gradient composite coatings in the embodiment of the present invention 1 based on 316 rustless steels in briny environment
Grinding defect morphology figure after frictional experiment；
Fig. 5 is the shape appearance figure of the polishing scratch exfoliation after white box region is amplified in Fig. 4；
Fig. 6 is the EDS test result figures in Fig. 5 at white box region.
Specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.It is pointed out that described below is implemented
Example is intended to be easy to the understanding of the present invention, and any restriction effect is not played to which.
Embodiment 1：
In the present embodiment, the compound painting of CrC multi-gradients on the stainless base steel sealing ring in the key components and partss of ocean, is prepared
Layer, preparation method are specific as follows：
(1) treatment before plating
Matrix is put into petroleum ether, is cleaned with ultrasonic stirring 15 minutes, after removing matrix surface greasy dirt, be put into acetone
It is middle to be cleaned by ultrasonic 15 minutes, subsequently it is cleaned by ultrasonic 15 minutes in dehydrated alcohol, finally taking-up is dried up with nitrogen；
(2) bias reverse sputtering cleaning
Matrix after step (1) process is loaded into multi-arc ion coating cavity, cavity temperature is 350 DEG C, and back end vacuum is taken out in advance
To 4.00 × 10-3Pa；Then, Ar gas of the purity more than or equal to 99.999% is passed through to cavity, Ar throughputs are 100sccm,
Matrix applies back bias voltage, successively constant bombardment matrix 3 minutes under the back bias voltage of -900V, -1100V and -1200V；
(3) Cr transition zones are deposited
With metal Cr of the purity more than or equal to 99.5% as target, 6 metal Cr targets are set in cavity, are continued to chamber
Body is passed through Ar gas, and argon flow amount is 350sccm, and operating air pressure is 0.4Pa；Apply deposition back bias voltage for -20V to matrix, Cr targets
Applying electric current is 60A, and depositing temperature is 350 DEG C, deposits 10min in matrix surface, obtains the thick Cr transition zones of about 0.2um；
(4) deposit CrN gradient transitional lay
Ar and N are passed through to cavity simultaneously2, Ar initial flows are set to 350sccm, terminate flow and be set to 0sccm, depositing
Uniformly reduce in journey；N2Initial flow is set to 0sccm, terminates flow and is set to 600sccm, uniformly increases in deposition process.To
It is -20V that matrix applies back bias voltage, and it is 60A that Cr targets apply electric current, and depositing temperature is 400 DEG C, deposits 10min in Cr layer surfaces, obtains
Obtain the thick CrN gradient transitional lay of about 0.2um；
(5) deposit CrCN gradient transitional lay
Cut-out Ar is flowed into, while being passed through N to cavity2And C2H2；N2Flow is set to 600sccm；C2H2Initial flow is set to
0sccm, terminates flow and is set to 100sccm, uniformly increase in deposition process.It is -20V, Cr to apply deposition back bias voltage to matrix
It is 60A that target applies electric current, and depositing temperature is 400 DEG C, deposits 30min in CrN layer surfaces, obtains the thick CrCN gradients of about 0.5um
Transition zone；
(6) CrC gradient top layers are deposited
Cut-out N2Flow into, while being passed through Ar and C to cavity2H2.Ar flows are fixed as 350sccm；C2H2Initial flow is set to
100sccm, terminates flow and is set to 150sccm, uniformly increase in deposition process.Cr target currents are raised to 60A, depositing temperature is protected
Hold at 400 DEG C, apply -200V biass to matrix, CrC gradient coatings, sedimentation time 120min are deposited in CrCN layer surfaces.
(7), after deposition to be coated terminates, less than 200 DEG C are cooled under vacuum environment, then protectiveness gas are filled with to cavity
Body N2, less than 100 DEG C are cooled under protective atmosphere, atmospheric pressure is deflated to, begin to speak to come out of the stove, CrC multilamellars are obtained in matrix surface
Gradient composite coating.
The section SEM test results of CrC multi-gradients composite coating obtained above as shown in Fig. 2 coating structure is fine and close,
Columnar growth is substantially suppressed, about 3.6 microns of coating layer thickness.
The glow discharge optical emission spectrometry test result of CrC multi-gradients composite coating obtained above is as shown in figure 3, in coating
Tri- kinds of constituent contents of Cr, C and N are consistent with the multilayered and graded structure design of the present invention along coating depth direction distribution gradient.
Grinding defect morphology of the CrC multi-gradients composite coating obtained above in briny environment after friction test and composition are surveyed
Test result is as Figure 4-Figure 6.As shown in Fig. 4 and 5, in polishing scratch, there is slight ditch dug with a plow, worn-out surface is integrally uniform, smooth, only
There is minimal amount of hole of peeling off to occur, white box region in such as Fig. 4.Fig. 5 is the polishing scratch stripping after white box region is amplified in Fig. 4
Fall the shape appearance figure at place.Energy spectrum analysiss, EDS test knots are carried out to the composition at the peeling hole inner white boxed area shown in Fig. 5
Fruit is as shown in fig. 6, find, in addition to Cr and C element in top layer, not detecting the letter of intermediate layer N element and matrix Fe elements
Number, illustrating that peeling hole depth is very limited, peeling is occurred over just inside top layer CrC layers.Further demonstrate that gradient components and many
Interfacial structure design can be with the diffusion of micro-crack in hinder coating and propagation, it is to avoid the formation of penetrability etching channels in coating,
Prevent sea water to matrix permeability, improve the medium corrosion resistance energy of coating.
Following performance test is carried out to CrC multi-gradients composite coating obtained above：
(1) the hard of the matrix surface coating is determined with continuous stiffness measurement in MTS-Nano G200 nanometers press-in test platform
Degree and elastic modelling quantity.Method of testing is：6 zoness of different are selected in coating surface, it is solid with the press-in of Berkovich diamond penetrators
Unload after depthkeeping degree 1000nm, obtain press-in-unloading curve, be calculated the hardness and elastic modelling quantity of coating, be then averaged
Value.Test obtains the coating hardness for 29GPa.
(2) the friction mill using UMT-3 multifunction friction wears testing machine to the matrix surface coating under atmospheric environment
Damage the life-span to be evaluated.Concrete grammar is：Mutually reciprocatingly slided mode with parafacies using plated film sealing ring cutting sample and friction, slided frequently
Rate is 5Hz, and load is 5N, ambient temperature (19 ± 3) DEG C, relative humidity (75 ± 5) %, the YG-6 sintered carbide balls of Φ=3mm
(its component and mass content are：94%WC and 6%Co, H ≈ 14GPa, E ≈ 650GPa) match somebody with somebody pair as friction.Measure the matrix
With wear rate as shown in table 1, average friction coefficient is 0.14 to the average friction coefficient of face coat, and wear rate is 2.3 × 10-15m3/N·m。
Embodiment 2：
In the present embodiment, matrix is identical with the matrix in embodiment 1, prepares CrC multi-gradients in the matrix surface
Composite coating, preparation method are specific as follows：
(1) it is identical with the step (1) in embodiment 1；
(2) it is identical with the step (2) in embodiment 1；
(3) it is identical with the step (3) in embodiment 1；
(4) it is identical with the step (4) in embodiment 1；
(5) deposit CrCN gradient transitional lay
Cut-out Ar is flowed into, while being passed through N to cavity2And C2H2。N2Flow is set to 600sccm；C2H2Initial flow is set to
0sccm, terminates flow and is set to 70sccm, uniformly increase in deposition process.Apply deposition back bias voltage for -20V to matrix, Cr targets
Applying electric current is 60A, and depositing temperature is 400 DEG C, deposits 30min in CrN layer surfaces, obtains the thick CrCN gradient mistakes of about 0.5um
Cross layer；
(6) CrC gradient top layers are deposited
Cut-out N2Flow into, while being passed through Ar and C to cavity2H2.Ar flows are fixed as 350sccm；C2H2Initial flow is set to
70sccm, terminates flow and is set to 120sccm, uniformly increase in deposition process.Cr target currents are raised to 60A, depositing temperature is protected
Hold at 400 DEG C, apply -200V biass to matrix, CrC gradient coatings, sedimentation time 120min are deposited in CrCN layer surfaces.
(7) it is identical with the step (6) in embodiment 1；.
The section SEM test results of CrC multi-gradients composite coating obtained above are similar to Figure 2, and coating structure is caused
Close, columnar growth is substantially suppressed, about 3.6 microns of coating layer thickness.
The glow discharge optical emission spectrometry test result of CrC multi-gradients composite coating obtained above is similar to Figure 3, in coating
Tri- kinds of constituent contents of Cr, C and N are consistent with the multilayered and graded structure design of the present invention along coating depth direction distribution gradient.
Following performance test is carried out to CrC multi-gradients composite coating obtained above：
(1) hardness test is identical with the testing procedure (1) in embodiment 1.Test obtains coating hardness and for hardness is
31GPa。
(2) friction and wear test is identical with the testing procedure (2) in embodiment 1.Measure the average of the matrix surface coating
As shown in table 1, average friction coefficient is 0.165 for coefficient of friction and wear rate, and wear rate is 1.9 × 10-15m3/N·m。
Embodiment 3：
In the present embodiment, matrix is identical with the matrix in embodiment 1, prepares CrC multi-gradients in the matrix surface
Composite coating, preparation method are specific as follows：
(1) it is identical with the step (1) in embodiment 1；
(2) it is identical with the step (2) in embodiment 1；
(3) it is identical with the step (3) in embodiment 1；
(4) it is identical with the step (4) in embodiment 1；
(5) deposit CrCN gradient transitional lay
Cut-out Ar is flowed into, while being passed through N to cavity2And C2H2。N2Flow is set to 600sccm；C2H2Initial flow is set to
0sccm, terminates flow and is set to 50sccm, uniformly increase in deposition process.It is -20V, Cr to apply deposition back bias voltage to matrix
It is 60A that target applies electric current, and depositing temperature is 400 DEG C, deposits 30min in CrN layer surfaces, obtains the thick CrCN gradients of about 0.5um
Transition zone；
(6) CrC gradient top layers are deposited
Cut-out N2Flow into, while being passed through Ar and C to cavity2H2.Ar flows are fixed as 350sccm；C2H2Initial flow is set to
50sccm, terminates flow and is set to 100sccm, uniformly increase in deposition process.Cr target currents are raised to 60A, depositing temperature is protected
Hold at 400 DEG C, apply -200V biass to matrix, CrC gradient coatings, sedimentation time 120min are deposited in CrCN layer surfaces.
(7) it is identical with the step (6) in embodiment 1；.
The section SEM test results of CrC multi-gradients composite coating obtained above are similar to Figure 2, and coating structure is caused
Close, columnar growth is substantially suppressed, about 3.6 microns of coating layer thickness.
The glow discharge optical emission spectrometry test result of CrC multi-gradients composite coating obtained above is similar to Figure 3, in coating
Tri- kinds of constituent contents of Cr, C and N are consistent with the multilayered and graded structure design of the present invention along coating depth direction distribution gradient.
Following performance test is carried out to CrC multi-gradients composite coating obtained above：
(1) hardness test is identical with the testing procedure (1) in embodiment 1.Measurement result shows the CrC/a-C composite coatings
Hardness be 34GPa.
(2) friction and wear test is identical with the testing procedure (2) in embodiment 1.Measure the average of the matrix surface coating
As shown in table 1, average friction coefficient is 0.192 for coefficient of friction and wear rate, and wear rate is 0.91 × 10-15m3/N·m。
Table 1：The sedimentary condition of CrC multi-gradients composite coating, hardness, average friction coefficient and abrasion in embodiment 1-3
Rate result
Embodiment described above has been described in detail to technical scheme, it should be understood that the above is only
For the specific embodiment of the present invention, the present invention is not limited to, all any modifications made in the spirit of the present invention,
Supplementary or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of chromium carbide multi-gradient composite coating of matrix surface, is characterized in that：Cr is stacked gradually upwards from matrix surface
Layer, CrN layers, CrCN layers, CrC layers.
2. the chromium carbide multi-gradient composite coating of matrix surface as claimed in claim 1, is characterized in that：In CrC layers, C
It is more than the stoichiometric proportion of CrC with the element ratio of Cr, in CrC with a-C Two-phase composite structures；
Preferably, along stacked direction, C element content gradually increases；It is highly preferred that in CrC layers, along stacked direction, C
Constituent content uniformly increases.
3. the chromium carbide multi-gradient composite coating of matrix surface as claimed in claim 1, is characterized in that：In CrN layers, edge
Stacked direction, N element content gradually increases；
Preferably, in CrN layers, along stacked direction, N element content uniformly increases；
Preferably, in CrCN layers, along stacked direction, C element content uniformly increases.
4. the chromium carbide multi-gradient composite coating of matrix surface as claimed in claim 1, is characterized in that：Described CrC layers
Thickness is 1 μm～10 μm；
Preferably, described Cr thickness degree is 100nm～500nm；Described CrN thickness degree is 100nm～500nm；It is described
CrCN thickness degree be 100nm～1 μm.
5. the chromium carbide multi-gradient composite coating of the matrix surface as described in any claim in Claims 1-4, which is special
Levying is：In more than 30GPa, wear rate is up to 10 for hardness-16m3/ Nm magnitudes；
Preferably, the average friction coefficient in atmospheric environment is below 0.2.
6. the system of the chromium carbide multi-gradient composite coating of the matrix surface as described in any claim in Claims 1-4
Preparation Method, is characterized in that：Using multi sphere ion plating technology, the matrix after surface cleaning processing is placed in into filming equipment vacuum cavity
In, with metal Cr as target, with high-purity Ar as working gas, with C2H2And N2For reacting gas, apply back bias voltage to matrix, it is right
Cr targets apply target current, deposit CrC multi-gradient composite coatings in matrix surface, specifically include following steps：
Step 1, Ar gases are passed through, Cr layers are deposited in matrix surface；
Step 2, continue to be passed through Ar gases, and be passed through N2, CrN layers are deposited in Cr layer surfaces；
Step 3, stopping are passed through Ar gases, continue to be passed through N2, and it is passed through C2H2, CrCN layers are deposited in Cr layer surfaces；
Step 4, stopping are passed through N2, continue to be passed through C2H2, and Ar is passed through, CrC layers are deposited in CrCN layer surfaces.
7. the preparation method of the chromium carbide multi-gradient composite coating of matrix surface as claimed in claim 6, is characterized in that：Institute
In the step of stating 1, Cr target currents are 40～80A, and substrate negative voltage is -20～-50V, sedimentation time 10min～30min；
Preferably, Ar flows are maintained at 200sccm～400sccm；
Preferably, heating-up temperature is 400 DEG C～450 DEG C.
8. the preparation method of the chromium carbide multi-gradient composite coating of matrix surface as claimed in claim 6, is characterized in that：Institute
In the step of stating 2, Cr target currents are 40～80A, and substrate negative voltage is -20～-50V, sedimentation time 10min～60min；
Preferably, Ar gas flows are gradually decreased, N2Gas flow gradually increases；Further preferably, Ar gases initial flow is
200sccm～400sccm, termination flow are 0sccm；N2Gas initial flow be 0sccm, terminations flow for 350sccm～
800sccm；It is highly preferred that in deposition process, Ar gas flows are uniformly reduced, N2Gas flow uniformly increases.
9. the preparation method of the chromium carbide multi-gradient composite coating of matrix surface as claimed in claim 6, is characterized in that：Institute
In the step of stating 3, Cr target currents are 40～80A, and substrate negative voltage is -20～-100V, sedimentation time 10min～60min；
Preferably, N2Gas flow is 350sccm～800sccm；
Preferably, C2H2Gas flow gradually increases；Further preferably, in deposition process, C2H2Gas initial flow is
0sccm, termination flow are 30sccm～100sccm；It is highly preferred that in deposition process, C2H2Gas flow uniformly increases.
10. the preparation method of the chromium carbide multi-gradient composite coating of matrix surface as claimed in claim 6, is characterized in that：
In described step 4, Cr target currents are 40～80A, and substrate negative voltage is -50～-300V, sedimentation time 1h～3h；
Preferably, Ar flows are maintained at 200sccm～400sccm；
Preferably, C2H2Initial flow is 50sccm～100sccm, and termination flow is 100sccm～200sccm；It is further excellent
Choosing, in deposition process, C2H2Gas flow gradually increases；It is highly preferred that in deposition process, C2H2Gas flow uniformly increases
Plus.
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