CN103451608B - A kind of diamond-like coating mixing tungsten and preparation method thereof - Google Patents
A kind of diamond-like coating mixing tungsten and preparation method thereof Download PDFInfo
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- CN103451608B CN103451608B CN201310344882.9A CN201310344882A CN103451608B CN 103451608 B CN103451608 B CN 103451608B CN 201310344882 A CN201310344882 A CN 201310344882A CN 103451608 B CN103451608 B CN 103451608B
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Abstract
The invention provides a kind of diamond-like coating mixing tungsten and preparation method thereof, this coating comprise be deposited on matrix surface Cr bottom, be prepared in the CrC transition layer on Cr bottom and be prepared in the diamond-like rock layers of mixing W on CrC transition layer.First matrix is carried out plasma clean during preparation, then column type electric arc Cr target is opened, Cr bottom is prepared at matrix surface, open planar magnetic control sputtering C target again, Cr bottom is prepared CrC transition layer, finally close column type electric arc Cr target, open planar magnetic control sputtering W target, on CrC transition layer, the diamond-like rock layers of W is mixed in preparation.The present invention adopts electric arc and magnetron sputtering composite film coating technology, the obtained smooth densification of coatingsurface, coating hardness is high, film-substrate cohesion is high, frictional coefficient is low, there is good anti-oxidant and chemical stability, the requirement of higher anti-oxidant and wear resistant friction reducing performance can be met, be with a wide range of applications.
Description
Technical field
The invention belongs to coated material preparation field, be specifically related to a kind of quasi-diamond (DLC) coating of mixing tungsten and preparation method thereof.
Background technology
Traditional carbon back superhard coating, as mixed Ti or mixing quasi-diamond (the Diamond-like Carbon of Cr, being called for short DLC) coating has the excellent properties such as high rigidity, low-friction coefficient, in component of machine surfacecti proteon field, there is wide application prospect, but the antioxidant property of these coatings is not enough, limit their further application.In recent years in order to reduce the fuel oil consumption of automobile and motorcycle engine, solving engine slide unit such as the wearing and tearing under high temperature operating conditions such as piston, piston ring and cylinder and oxidation deactivation and just becoming more and more important.In addition, the component surface of the high-speed motion such as crankshaft of cooler compressor, slide block also needs coating to have oxidation resistant wear resistant friction reducing coating.Obviously, above-mentioned traditional carbon-base coating is difficult to meet the demands.
At present, carbon back superhard coating mainly adopts magnetron sputtered deposition technology to prepare, the method has composition regulation and control and composition optimizes convenience, and rete is fine and close and surface smoothness advantages of higher, but it is not high that the main drawback of magnetron sputtering technique is coating binding force, sedimentation rate is comparatively slow, is difficult to meet the workpiece surface strengthening requirement under harsh service condition.Electric arc ion coating plating technology of preparing has that sedimentation rate is fast, bonding force advantages of higher, is mainly used at present in cutter and mold facecoat preparation.But the drop in electric arc ion coating plating is due to the restriction of preparation principle itself, cannot thoroughly eliminate all the time, causes coating structure comparatively loose, surfaceness difference etc.
Summary of the invention
The object of the present invention is to provide a kind of diamond-like coating mixing tungsten and preparation method thereof, this diamond-like coating smooth surface of mixing tungsten is fine and close, and coating hardness is strong, can meet anti-oxidant and requirement that is wear resistant friction reducing performance.
In order to achieve the above object, the technical solution used in the present invention is:
Mix a diamond-like coating for tungsten, comprise be deposited on matrix surface Cr bottom, be prepared in the CrC transition layer on Cr bottom and be prepared in the diamond-like rock layers of mixing W on CrC transition layer.
Described Cr bottom is obtained by electric arc ion coating plating method, and CrC transition layer is obtained by electric arc ion coating plating method and magnetically controlled sputter method, and the diamond-like rock layers of mixing W is obtained by magnetically controlled sputter method.
Its thickness is 2.0 μm, and hardness is 28GPa, and film-substrate cohesion is 70N, and oxidation resistance temperature reaches 800 DEG C; When friction pair is Si
3n
4during ball, its dry friction coefficient is 0.1.
Mix a preparation method for the diamond-like coating of tungsten, comprise the following steps:
1) matrix plasma clean: the vacuum chamber matrix that pre-treatment is good being put into electric arc and magnetron sputtering composite coating equipment, passes into Ar and carries out Bombardment and cleaning to matrix surface after vacuumizing;
2) preparation of Cr bottom: after step 1) completes, regulates argon flow amount to make gas pressure in vacuum be 0.3Pa, then opens column type electric arc Cr target, prepares Cr bottom at matrix surface;
3) preparation of CrC transition layer: in step 2) complete after, column type electric arc Cr target is held open state, opens planar magnetic control sputtering C target, Cr bottom is prepared CrC transition layer;
4) preparation of the diamond-like rock layers of W is mixed: after step 3) completes, column type electric arc Cr target is closed, the power of planar magnetic control sputtering C target is adjusted to 5KW, the power of planar magnetic control sputtering W target is increased to 3KW by 0, on CrC transition layer, the diamond-like rock layers of W is mixed in preparation, obtains the diamond-like coating mixing tungsten.
Described matrix is that the hardness after 550 DEG C of tempering is the high speed steel substrate of HRC=60 through 1170 DEG C of quenchings, and its material is W
18cr
4v.
The pre-treatment of described matrix is: immerse ultrasonic cleaning in acetone by after matrix surface oil removing, polishing, then dehydration of alcohol.
Vacuumize in described step 1) and be first heated to 300 DEG C afterwards, pass into Ar again and Bombardment and cleaning is carried out to matrix surface, the concrete operations of Bombardment and cleaning are: pass into the Ar of 10ml/min to vacuum chamber, when gas pressure in vacuum reaches 6Pa, open and be biased into-1000V Bombardment and cleaning is carried out to the matrix surface in vacuum chamber, continue 30min.
Described step 2) in regulate argon flow amount be 30ml/min thus make gas pressure in vacuum be 0.3Pa, the concrete operations preparing Cr bottom at matrix surface are: the electric current of column type electric arc Cr target is 50A, and bias voltage be-300V, maintenance 10min.
The concrete operations preparing CrC transition layer in described step 3) on Cr bottom are: the electric current maintaining column type electric arc Cr target is 50A, and bias voltage is-300V, and the power of planar magnetic control sputtering C target is 3KW, continues 30min.
The vacuum chamber temperature of mixing in described step 4) in the preparation process of the diamond-like rock layers of W is 150 DEG C, and bias voltage is-300V, and air pressure is 1.5Pa, and depositing time is 150min.
Relative to prior art, beneficial effect of the present invention is:
Present invention utilizes the antioxidant property that refractory metal tungsten (W) is good, provide a kind of diamond-like coating mixing tungsten with transition layer structure, this is mixed, and the diamond-like coating smooth surface of tungsten is fine and close, coating hardness is high, film-substrate cohesion is high, frictional coefficient is low, also there is good anti-oxidant and chemical stability, the requirement of higher anti-oxidant and wear resistant friction reducing performance can be met, be expected to the anti-oxidant of the engine component realizing automobile and motorcycle and wear resistant friction reducing performance requriements, be with a wide range of applications.
The present invention adopts electric arc and magnetron sputtering composite film coating technology HAMSD(HybridArc-Magnetron Sputtering Deposition), utilize the advantage of magnetron sputtering rete densification, and arc ion plating rete bonding force is high and the advantage of fast growth, and have employed the method for design of bottom and transition layer, first at substrate deposit Cr bottom, CrC transition layer is prepared again on Cr bottom, finally on CrC transition layer, the diamond-like rock layers of W is mixed in preparation, finally obtain the diamond-like coating mixing tungsten, the prepared diamond-like coating smooth surface of mixing tungsten is fine and close, the hardness of coating is high, film-substrate cohesion is strong, dry friction coefficient is low, oxidation resistance temperature is high.The diamond-like coating showing to mix tungsten has good antioxidant property and wear resistant friction reducing performance.
Further, adopt the diamond-like coating mixing tungsten prepared by method of the present invention, its thickness is 2.0 μm after measured, and hardness is 28GPa, and film-substrate cohesion is 70N, and oxidation resistance temperature reaches 800 DEG C;
When friction pair is Si
3n
4during ball, its dry friction coefficient is 0.1.
Accompanying drawing explanation
Fig. 1 is the structural representation of electric arc of the present invention and magnetron sputtering composite coating equipment;
Fig. 2 is that the scanning cross-section pattern SEM mixing the diamond-like coating of tungsten prepared by the present invention schemes;
Wherein: 1 be vacuum chamber, 2 be turntable frame, 3 be bias voltage, 4 be rotating stand rod, 5 be planar magnetic control sputtering C target or planar magnetic control sputtering W target, 6 be permanent magnet, 7 be column type electric arc Cr target, 8 be well heater, 9 be pump group.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The diamond-like coating mixing tungsten provided by the invention, comprise be deposited on matrix surface Cr bottom, be prepared in the CrC transition layer on Cr bottom and be prepared in the diamond-like rock layers of mixing W on CrC transition layer.Cr bottom is obtained by column type electric arc Cr target (electric arc ion coating plating method), CrC transition layer is obtained by column type electric arc Cr target and plane magnetron sputtering C target (electric arc ion coating plating method and magnetically controlled sputter method), and the diamond-like rock layers of mixing W is obtained by planar magnetic control sputtering W target and plane magnetron sputtering C target (magnetically controlled sputter method).
Embodiment 1 provides a kind of method of mixing the diamond-like coating of tungsten in surface of high speed steel preparation, it should be noted that, the diamond-like coating of prepared by method of the present invention mix tungsten, can carry out, be not limited to this embodiment on any black or nonferrous metal material surface.
Embodiment 1
(1) substrate pretreated: adopt through 1170 DEG C of quenchings, the hardness after 550 DEG C of tempering is the high speed steel substrate (material: W of HRC=60
18cr
4v) as matrix, ultrasonic cleaning in acetone is immersed by after its surface degreasing, polishing, then dehydration of alcohol.
(2) matrix that pre-treatment is good is put into the vacuum chamber of electric arc and magnetron sputtering composite coating equipment rotating stand rod on.As shown in Figure 1, electric arc and magnetron sputtering composite coating equipment at least comprise vacuum chamber 1, turntable frame 2, bias voltage 3, rotating stand rod 4, planar magnetic control sputtering C target or planar magnetic control sputtering W target 5, permanent magnet 6, column type electric arc Cr target 7, well heater 8, pump group 9, rotating stand rod 4 can be rotated with turntable frame 2, also can rotation, doing so avoids film can only one side plating and the problem of plated film inequality, ensure that the homogeneity of coating process.
(3) adopt φ 60 × 495mm column type electric arc Cr target 7 as the Cr source of prime coat and transition layer, effectively improve film-substrate cohesion, by the sputtering raste of the current control post arc Cr target 7 of column type electric arc Cr target; Three pairs of plane magnetic controlled sputtering targets that employing is of a size of 435 × 95 × 10mm (are for a pair wherein planar magnetic control sputtering W target, two pairs is planar magnetic control sputtering C target) as the source of corresponding W or C element, as shown in Figure 1, three pairs of plane magnetic controlled sputtering targets 5 to be placed on the inwall of electric arc and magnetron sputtering composite coating equipment the mode of target, and pass through the sputtering raste of the power control plane magnetron sputtering target of adjustment medium-frequency pulse power supply; Adopt high-purity Ar as ionization of gas, ensure effective glow discharging process, mix the diamond-like coating of tungsten at matrix surface formation of deposits.
(4) preparation process condition of the diamond-like coating of tungsten is mixed:
A) matrix plasma clean:
After matrix is loaded vacuum chamber, to vacuumize and to be heated to maintenance 300 DEG C constant, the Ar then passing into 10ml/min, to vacuum chamber, when gas pressure in vacuum reaches 6Pa, opens and is biased into-1000V and carries out Bombardment and cleaning to the matrix surface in vacuum chamber, continue 30min.
B) preparation of Cr bottom:
In steps A) complete after, regulate argon flow amount to 30ml/min, thus gas pressure in vacuum is adjusted to 0.3Pa, then open column type electric arc Cr target, the electric current of column type electric arc Cr target is 50A, adjusts and is biased into-300V and keeps 10min, prepare Cr bottom at matrix surface.
C) preparation of CrC transition layer:
After prepared by Cr bottom, keep the electric current of column type electric arc Cr target to be that 50A and bias voltage are constant for-300V, open the control power supply of planar magnetic control sputtering C target, the power of planar magnetic control sputtering C target is adjusted to 3KW, Cr bottom is prepared CrC transition layer, continues 30min.
D) preparation of the diamond-like rock layers of W is mixed:
After prepared by CrC transition layer, column type electric arc Cr target is closed, the power of planar magnetic control sputtering C target is adjusted to 5KW, the power of planar magnetic control sputtering W target is increased to 3KW by 0 gradually, on CrC transition layer, the diamond-like rock layers of W is mixed in preparation, and mixing vacuum chamber temperature in the diamond-like rock layers preparation process of W is 150 DEG C, and bias voltage is-300V, air pressure is 1.5Pa, and depositing time is 150min.
Under above-mentioned processing condition, can obtain smooth surface densification, coat-thickness is the diamond-like coating mixing tungsten of 2.0 μm.The scanning electron microscope morphology of this coating vertical section as shown in Figure 2, can be found out, coating structure is fine and close, obvious with the line of delimitation of matrix.After tested, the hardness 28GPa mixing the diamond-like coating of tungsten prepared, film-substrate cohesion 70N, coat-thickness 2.0 μm.When friction pair is Si
3n
4during ball, the dry friction coefficient mixing the diamond-like coating of tungsten is 0.1, and the oxidation resistance temperature mixing the diamond-like coating of tungsten reaches 800 DEG C, and the diamond-like coating showing to mix tungsten has good antioxidant property and wear resistant friction reducing performance.
Claims (4)
1. mix a preparation method for the diamond-like coating of tungsten, it is characterized in that, comprise the following steps:
1) matrix plasma clean: the vacuum chamber matrix that pre-treatment is good being put into electric arc and magnetron sputtering composite coating equipment, passes into Ar and carries out Bombardment and cleaning to matrix surface after vacuumizing;
2) preparation of Cr bottom: in step 1) complete after, adjustment argon flow amount is 30mL/min, makes gas pressure in vacuum be 0.3Pa, then open column type electric arc Cr target, the electric current of column type electric arc Cr target is 50A, and bias voltage is-300V, keep 10min, prepare Cr bottom at matrix surface;
3) preparation of CrC transition layer: in step 2) complete after, column type electric arc Cr target is held open state, the electric current maintaining column type electric arc Cr target is 50A, bias voltage is-300V, open planar magnetic control sputtering C target, the power of planar magnetic control sputtering C target is 3KW, continues 30min, Cr bottom is prepared CrC transition layer;
4) mix the preparation of the diamond-like rock layers of W: in step 3) complete after, column type electric arc Cr target is closed, the power of planar magnetic control sputtering C target is adjusted to 5KW, the power of planar magnetic control sputtering W target is increased to 3KW by 0, and on CrC transition layer, the diamond-like rock layers of W is mixed in preparation, obtains the diamond-like coating mixing tungsten, the vacuum chamber temperature of wherein mixing in the preparation process of the diamond-like rock layers of W is 150 DEG C, bias voltage is-300V, and air pressure is 1.5Pa, and depositing time is 150min.
2. the preparation method mixing the diamond-like coating of tungsten according to claim 1, is characterized in that: described matrix is that the hardness after 550 DEG C of tempering is the high speed steel substrate of HRC=60, and its material is W through 1170 DEG C of quenchings
18cr
4v.
3. the preparation method mixing the diamond-like coating of tungsten according to claim 1, is characterized in that: the pre-treatment of described matrix is: immerse ultrasonic cleaning in acetone by after matrix surface oil removing, polishing, then dehydration of alcohol.
4. according to the preparation method mixing the diamond-like coating of tungsten in claim 1-3 described in any one, it is characterized in that: described step 1) in vacuumize and be first heated to 300 DEG C afterwards, pass into Ar again and Bombardment and cleaning is carried out to matrix surface, the concrete operations of Bombardment and cleaning are: pass into the Ar of 10ml/min to vacuum chamber, when gas pressure in vacuum reaches 6Pa, open and be biased into-1000V Bombardment and cleaning is carried out to the matrix surface in vacuum chamber, continue 30min.
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