CN106086886B

CN106086886B - A kind of self-lubricating titanium diboride/diamond-like carbon coating and its preparation method and application

Info

Publication number: CN106086886B
Application number: CN201610654843.2A
Authority: CN
Inventors: 高翔; 代伟; 王启民
Original assignee: Guangdong University of Technology
Current assignee: Guangdong University of Technology
Priority date: 2016-08-10
Filing date: 2016-08-10
Publication date: 2019-06-14
Anticipated expiration: 2036-08-10
Also published as: CN106086886A

Abstract

The invention discloses a kind of self-lubricating titanium diboride (TiB₂)/Diamond-like Carbon (DLC) hard coat and preparation method thereof.The TiB₂/ DLC hard coat is to use bipolar pulse magnetron sputtered deposition technology in substrate by TiB₂Ceramic layer is periodically overlapped mutually with DLC layer, TiB₂The modulation period of/DLC hard coat is 15~60nm, and total coating thickness is 1.2~1.4 μm.TiB of the present invention₂/ DLC hard coat combines TiB₂With the advantage of DLC respectively, with excellent hardness and lubrication property, and there is good electric conductivity, the pulsed magnetron sputtering deposition technique used simultaneously is easy to operate, simple process, short preparation period are at low cost, convenient for large-scale industrial production, it can be widely applied to the fields such as cutter, mold, microelectronics, protection.

Description

A kind of self-lubricating titanium diboride/diamond-like coating and its preparation method and application

Technical field

The invention belongs to surface protection technique and related coatings technical fields, are related to a kind of laminated coating of self-lubricating, more In particular it relates to a kind of titanium diboride (TiB with high rigidity, the periodic multilayer structure of low-friction coefficient₂)/diamond-like (DLC) coating and its preparation method and application.

Background technique

With the development of society and the progress of industrial technology, industrial circle proposes higher and higher want to the performance of material It asks, there is excellent comprehensive performance in many engineer application application requirements materials；It is not required nothing more than with high hardness, corrosion-resistant Performance also requires it with low coefficient of friction, good high-temperature stability etc..To meet increasingly complicated and diversified engineering need It asks, coats one layer of hard coat on the surface of the material, come into being with improving the protective coating of comprehensive performance of material.Hard applies Layer can improve the surface property of material, reduce the friction and wear with workpiece, the effective material surface hardness, toughness, resistance to of improving Mill property and high-temperature stability, increase substantially the service life of coating product.Hard coat is improve material surface property one The economical and practical means of kind, are being machined at present, are especially occupying an important position in metal cutting.Its development adapts to High-tech requirement of the modern manufacturing industry to metal cutting tool, causes the great change of cutter material and performance, can be widely used In fields such as machine-building, auto industry, textile industry, geological drilling, mould industry, aerospaces.

Titanium diboride (TiB₂) it is used as magnesium-yttrium-transition metal boride, there is high rigidity, high-melting-point, high wearability and corrosion resistant Corrosion, good conductivity and a series of excellent physicochemical properties such as thermal conductivity, chemical stability be excellent, be it is a kind of have it is excellent Structural behaviour and functional performance advanced ceramics material.Diamond-like coating (DLC) is that one kind contains gold in microstructure The coating of hard rock ingredient.The element for constituting DLC is carbon, with sp between carbon atom and carbon atom³And sp²Strong form combines, due to Containing diamond components, DLC has many excellent characteristics, such as: high rigidity, low-friction coefficient, fabulous film layer compactness, Good chemical stability and good optical property etc..The property shown applied to the DLC coating on cutter Far more than other hard coats.

Titanium diboride is easy to produce crackle when being impacted and the failure that falls off since toughness is poor, causes it as protection The service efficiency and application field of coating are restricted.Currently used hard coat toughening mode has multilayered structure toughening and soft Matter Xiang Zengren.Due to being limited by structure and doping content, making coating performance is in periodically to change and unstable, Huo Zheren Property improve while hardness decline it is very big.Therefore, it explores and can be realized the hard and tough coating skill urgently to be resolved as this field Art problem.

Summary of the invention

The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of high rigidity, low stress, low friction system Excellent toughness is counted and had, can apply to the multilayer hard protective coating of the product surfaces such as component of machine, knife mold.Adopt Use TiB₂With the combination of DLC, by TiB₂What layer and DLC layer alternating deposit were formed on matrix has high rigidity and high friction resistance The hard coat of the periodic multilayer structure of energy.

Another mesh of the invention is to provide above-mentioned self-lubricating titanium diboride TiB₂The system of/diamond-like DLC hard coat Preparation Method, the preparation method have easy to operate, simple process, and short preparation period is at low cost, are convenient for large-scale industrial production The advantages that.

Still a further object of the present invention is to provide above-mentioned self-lubricating titanium diboride TiB₂/ diamond-like DLC hard coat cutter, Application in mold, microelectronics and protection field.

Above-mentioned purpose of the present invention is to be achieved by the following technical programs:

A kind of self-lubricating titanium diboride TiB₂/ diamond-like DLC coating, the TiB₂/ DLC coating is with TiB₂Ceramic target It is raw material with graphite target, replaces sputtering sedimentation on matrix by multi-target magnetic control sputtering and formed by TiB₂Nano-ceramic layer and DLC Nanometer layer is periodically overlapped mutually.

Preferably, the TiB₂Ceramic target is flat target, and the atomic ratio of Ti and B are 1:2, purity 99.99%；Graphite target For Style Columu Talget, purity 99.99%.

Preferably, described matrix is one of hard alloy, monocrystalline silicon piece, alumina wafer or glass.

Preferably, described matrix and TiB₂Nanometer layer contact, the DLC nanometer layer are outermost layer, TiB₂/ DLC hard coat Overall thickness is 1.2~1.4 μm.

Preferably, the DLC layer with a thickness of 5~10nm/ layers, TiB₂Layer with a thickness of 10~50nm/ layers, the TiB₂/ DLC and TiB in DLC hard coat₂Total number of plies be 20~80 layers.

A kind of above-mentioned self-lubricating TiB₂The preparation method of/DLC hard coat, comprises the following specific steps that:

S1. it cleans matrix: polished treated matrix being sent into supersonic wave cleaning machine, successively uses acetone, dehydrated alcohol 10~20min of ultrasonic cleaning is carried out respectively with 15~30kHz, is then cleaned with deionized water, then with the nitrogen of purity >=99.5% Air-blowing is dry；

S2. it vacuumizes and cleans plated film cavity with ion beam etching: the matrix after ultrasonic cleaning is placed in the workpiece of vacuum chamber On bracket, it is evacuated to vacuum degree 5.0 × 10^-3Pa is passed through 80~100sccm argon gas to ion source hereinafter, later on ion source, if The power for setting ion source is 0.9kW, and the bias that work support is arranged is -300~-500V, etch cleaner process continues 20~ 30min；

S3. ion beam etching matrix: by matrix as in front of ion source, setting bias is -300~-500V, working time For 15~20min；

S4.TiB₂The preparation of/DLC hard coat: using the method for bipolar pulse magnetron sputtering, matrix and bracket ginseng are set Number, target are passed through 80~100sccm of argon gas at a distance from matrix, control 0.5~0.6Pa of gas pressure in vacuum, open and electricity is arranged Source parameter, wherein TiB₂Ceramic target is A target, and graphite target is B target, by sample baffle transposition in TiB₂Before ceramic target and graphite target, rise Brightness after 10~15min of pre-sputtering, opens sample baffle, starts sputtering sedimentation TiB₂/ DLC hard coat, sputtering time 3h.

S5. deposition terminates, and closes power supply, is down to room temperature to vacuum room temperature, fills atmosphere toward vacuum chamber, opens vacuum chamber and takes Sample out forms TiB in matrix surface₂/ DLC hard coat.

Preferably, matrix described in step S4 and support parameter are as follows: substrate bias -100~-300V, bracket rotation 3rpm/ Min, revolve 2~5rpm/min, is arranged 300 DEG C of depositing temperature.

Preferably, power parameter described in step S4 are as follows: frequency 40kHz, 3~4kW of power, the A target pulse power account for Sky is than being 25~75%.

Preferably, target described in step S4 is 6~10cm at a distance from matrix.

Above-mentioned self-lubricating titanium diboride/diamond-like hard coat is in the surfacecti proteon field of cutter, mold and microelectronics In application it is also within the scope of the present invention.

Compared with prior art, the invention has the following advantages:

1. TiB of the invention₂/ DLC hard coat has periodic multilayered structure, has not only had high rigidity but also has had good Toughness, while anti-friction, polishing machine, electric conductivity and resistance to chemical corrosion show good TiB₂/ DLC hard applies Layer.Wherein, TiB₂With hexagonal crystallographic texture and (001) preferred orientation；DLC layer contains a certain number of SP³Key.Due to being added DLC layer makes TiB₂/ DLC coating has high rigidity and lower coefficient of friction, is lower than with the coefficient of friction of GCr15 steel ball 0.30, to show excellent crocking resistance, can be used as protective coating for high friction resistance energy and high rigidity Engineering applications, can be used for the surfacecti proteon field of cutter, mold, microelectronics.

2. the TiB that present invention preparation has nanometer laminated structure₂/ DLC hard coat, easy to operate, simple process, preparation Period is short, at low cost, is convenient for large-scale industrial production.

Detailed description of the invention

Fig. 1 is TiB prepared by embodiment 1₂/ DLC coating structure schematic diagram.

Fig. 2 is TiB prepared by embodiment 1₂/ DLC coating XRD diagram.

Fig. 3 is TiB prepared by embodiment 1₂The surface SEM of/DLC coating schemes.

Fig. 4 is TiB prepared by embodiment 1₂The scratch shape appearance figure of/DLC coating.

Specific embodiment

The contents of the present invention are further illustrated with specific embodiment with reference to the accompanying drawings of the specification, but should not be construed as to this The limitation of invention.Unless otherwise specified, the conventional hand that technological means used in embodiment is well known to those skilled in the art Section.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.

Embodiment 1

1. preparation:

S1. it cleans matrix: polished treated WC-Co hard alloy matrix being sent into supersonic wave cleaning machine, is successively used Acetone, dehydrated alcohol carry out ultrasonic cleaning 10min with 30kHz respectively, are then cleaned with deionized water, then with purity >=99.5% Be dried with nitrogen.

S2. vacuumize and ion beam etching cleaning chamber and matrix: ion plating equipment installs TiB₂Flat target and graphite column Shape target cleans coating chamber with high power dust catcher.Matrix after ultrasonic cleaning is placed on the work support of vacuum chamber, is evacuated to true Reciprocal of duty cycle 5.0 × 10^-3Pa is passed through 80sccm argon gas to ion source, ion source power 0.9kW is arranged hereinafter, later on ion source, Work support bias -300V is set, this etching cleaning process continues 20min.

S3. ion beam etching matrix: rotation pivoted frame, by matrix as in front of ion source, being arranged bias -500V, when work Between be 20min.

S4. it is passed through argon gas 80sccm, controls gas pressure in vacuum 0.56Pa, using the method for bipolar pulse magnetron sputtering, TiB₂Ceramic target is A target, and graphite target is B target, and target is 10cm at a distance from matrix, matrix and support parameter is arranged are as follows: matrix Bias -100V, bracket rotation 3rpm/min, revolve 2rpm/min, is arranged 300 DEG C of depositing temperature.It opens and power parameter is set Are as follows: frequency 40kHz, power 4kW, A target pulse power duty ratio be 75%.By sample baffle transposition in two sputtering targets Before, build-up of luminance after carrying out pre-sputtering 10min, opens sample baffle, starts formal sputtering depositing Ti B₂/ DLC laminated coating, deposition Time is 3h.

S5. deposition terminates, and closes power supply, is down to room temperature to vacuum room temperature, fills atmosphere toward vacuum chamber, opens vacuum chamber and takes Sample out forms the TiB of periodic multilayer structure in WC-Co hard alloy matrix surface₂/ DLC coating.

2. performance test:

Fig. 1 is TiB₂/ DLC coating structure schematic diagram.Wherein, DLC layer with a thickness of 5~10nm/ layers, TiB₂The thickness of layer It is 10~50nm/ layers, TiB₂DLC and TiB in/DLC hard coat₂Total number of plies be 20~80 layers.Fig. 2 is TiB₂/ DLC coating XRD diagram, it can be seen that TiB₂Well-crystallized has 001 preferred orientation, and DLC is amorphous state.Fig. 3 is TiB₂/ DLC coating Surface SEM figure, it can be seen that coating surface is smooth, without apparent particle agglomeration, the results showed that coating surface growth is good It is good, dense uniform.

By the TiB of preparation₂/ DLC coating sample carries out analysis test, with Anton Paar NHT2 type nano-hardness tester testing coating Hardness and elastic modulus, the results showed that, TiB₂/ DLC coating shows good toughness, and elastic resilience is up to 50%；It measures Coating hardness reaches 35Gpa；Measuring coefficient of friction with HSR-2M coating friction wear testing machine is 0.19, after sample wears 1h, Have no failure, it is seen that TiB₂/ DLC coating has good wear Characteristics.It is residual that coating is measured with the general membrane stress instrument of speed Overbottom pressure stress 0.5Gpa；With Anton Paar MST type nano impress instrument, test results are shown in figure 4, Fig. 4 TiB₂/ DLC coating is drawn Trace shape appearance figure.There it can be seen that scratch increases with load, scratch gradually broadens, and load increases depth and increases, around scratch Without film layer obscission, and without cracked in scoring groove, the more smooth groove of appearance, the results showed that in Hardness loss TiB in the case where less₂/ DLC coating shows preferable toughness.Coated film base junction closes critical load and reaches 10GPa, coating attachment It has excellent performance；Finally by obtained TiB₂/ DLC coating carries out acid-fast alkali-proof corrosion test at normal temperature, the results showed that, TiB₂/ DLC coating has good chemical stability.

Embodiment 2

S1. it cleans matrix: the polished single crystal silicon substrate that treated (100) is orientated is sent into supersonic wave cleaning machine, according to It is secondary that ultrasonic cleaning 10min is carried out respectively with 30kHz with acetone, dehydrated alcohol, then rinsed with deionized water, then with purity >= 99.5% is dried with nitrogen.

S2. vacuumize and ion beam etching cleaning chamber and matrix: ion plating equipment installs TiB₂Flat target and graphite column Shape target cleans coating chamber with high power dust catcher.Matrix after ultrasonic cleaning is placed on the work support of vacuum chamber, vacuum chamber It vacuumizes, until vacuum 5.0 × 10^-3Pa is passed through 80sccm argon gas to ion source, ion source is arranged hereinafter, later on ion source Work support bias 300V is arranged in power 0.9kW, this etching cleaning process continues 20min.

S4. it is passed through argon gas 80sccm, controls gas pressure in vacuum 0.56Pa, using the method for bipolar pulse magnetron sputtering, TiB₂Ceramic target is A target, and graphite target is B target, and target is 6cm at a distance from matrix, matrix and support parameter is arranged are as follows: matrix is inclined Pressure -300V, bracket rotation 3rpm/min, revolve 5rpm/min, is arranged 300 DEG C of depositing temperature.It opens and power parameter is set are as follows: Frequency 40kHz, power 4kW, A target pulse power duty ratio be 25%.By sample baffle transposition before two sputtering targets, rise Brightness after carrying out pre-sputtering 15min, opens sample baffle, starts formal sputtering depositing Ti B₂/ DLC laminated coating, sedimentation time 3h。

S5. deposition terminates, and closes power supply, is down to room temperature to vacuum room temperature, inflates toward vacuum chamber, opens vacuum chamber and takes out Sample forms the TiB of periodic multilayer structure on the single crystal silicon substrate surface of (100) orientation₂/ DLC coating.

The above embodiment of the present invention only to clearly illustrate example of the present invention, and is not to reality of the invention Apply the restriction of mode.For those of ordinary skill in the art, it can also make on the basis of the above description other Various forms of variations.There is no necessity and possibility to exhaust all the enbodiments.It is all in the spirit and principles in the present invention Within made any modifications, equivalent replacements, and improvements etc., should all be included in the scope of protection of the claims of the present invention.

Claims

1. a self-lubricating titanium diboride/diamond-like coating is characterized in that, the titanium diboride/diamond-like coating is TiB ₂ /DLC coating, and is based _on TiB ceramic target and graphite target. The raw material is formed by alternately sputtering deposition on the substrate by multi-target magnetron sputtering, which is formed by the periodic superposition of the TiB ₂ nano-ceramic layer and the DLC nano-layer;

The preparation method of the self-lubricating TiB ₂ /DLC coating comprises the following specific steps:

(1) Cleaning the substrate: The polished substrate is sent to an ultrasonic cleaner, followed by ultrasonic cleaning with acetone and absolute ethanol at 15 to 30 kHz for 10 to 20 minutes, then cleaned with deionized water, and then with a purity of ≥99.5 % nitrogen blow dry;

(2). Vacuuming and ion beam etching to clean the coating cavity: place the ultrasonically cleaned substrate on the workpiece support of the vacuum chamber, and pump the vacuum to below 5.0×10 ^-3 Pa. The source is fed with 80-100sccm argon gas, the power of the ion source is set to 0.9kW, the bias voltage of the workpiece support is set to -300--500V, and the etching and cleaning process lasts for 20-30min;

(3) Ion beam etching substrate: place the substrate in front of the ion source, set the bias voltage to -300～-500V, and set the working time to 15～20min;

(4) Preparation of TiB ₂ /DLC hard coating: Bipolar pulsed magnetron sputtering method was adopted, 80-100 sccm of argon gas was introduced, the pressure of vacuum chamber was controlled to 0.5-0.6 Pa, and the sample baffle was transferred to TiB ₂ Before the ceramic target and the graphite target, ignite, and after 10-15 minutes of pre-sputtering, open the sample shutter and start sputtering deposition of TiB ₂ /DLC hard coating. The sputtering time is 3h;

(5) After the deposition is completed, turn off the power supply, and when the temperature of the vacuum chamber drops to room temperature, fill the vacuum chamber with air, open the vacuum chamber to take out the sample, and form a TiB ₂ /DLC coating on the surface of the substrate.

2. The self-lubricating titanium diboride/diamond-like carbon coating according to claim ₁ , wherein the TiB ceramic target is a flat target, the atomic ratio of Ti and B is 1:2, and the purity is 99.99% ; The graphite target is a columnar target with a purity of 99.99%.

3 . The self-lubricating titanium diboride/diamond-like carbon coating according to claim 1 , wherein the substrate is one of cemented carbide, single crystal silicon wafer, alumina wafer or glass. 4 .

4. The self-lubricating titanium diboride/diamond-like carbon coating of claim 1, wherein the substrate is in contact with the TiB ₂ nanometer layer, the DLC nanometer layer is the outermost layer, and the TiB ₂ /DLC coating The total thickness is 1.2 to 1.4 μm.

5. The self-lubricating titanium diboride/diamond-like carbon coating according to claim ₁ , wherein the thickness of the DLC layer is 5-10 nm/layer, the thickness of the TiB layer is 10-50 nm/layer, and the thickness of the DLC layer is 5-10 nm/layer. The total number of layers of DLC and TiB ₂ in the TiB ₂ /DLC coating is 20 to 80 layers.

6. a preparation method of self-lubricating TiB ₂ /DLC coating according to any one of claims 1-5, is characterized in that, comprises the following concrete steps:

S1. Cleaning the substrate: The polished substrate is sent to an ultrasonic cleaner, followed by ultrasonic cleaning with acetone and absolute ethanol at 15 to 30 kHz for 10 to 20 minutes, then cleaned with deionized water, and then with a purity of ≥99.5% dry with nitrogen;

S2. Evacuation and ion beam etching to clean the coating cavity: place the ultrasonically cleaned substrate on the workpiece support of the vacuum chamber, evacuate to a degree of vacuum below 5.0×10 ^-3 Pa, then turn on the ion source, and connect to the ion source. Enter 80～100sccm argon gas, set the power of the ion source to 0.9kW, set the bias voltage of the workpiece support to be -300～-500V, and the etching and cleaning process lasts for 20～30min;

S3. Ion beam etching substrate: place the substrate in front of the ion source, set the bias voltage to -300～-500V, and set the working time to 15～20min;

S4. Preparation of TiB ₂ /DLC hard coating: adopt the method of bipolar pulsed magnetron sputtering, set the parameters of the substrate and the support, the distance between the target and the substrate, pass argon gas to 80-100 sccm, and control the vacuum chamber pressure to 0.5 ～0.6Pa, turn on and set the power parameters, in which the TiB ₂ ceramic target is the A target and the graphite target is the B target, and the sample baffle is placed in front of the TiB ₂ ceramic target and the graphite target, ignited, and pre-sputtered for 10 to 15 minutes After that, open the sample shutter and start sputtering deposition of TiB ₂ /DLC hard coating, and the sputtering time is 3h;

S5. After the deposition is completed, turn off the power supply, and when the temperature of the vacuum chamber drops to room temperature, fill the vacuum chamber with air, open the vacuum chamber to take out the sample, and form a TiB ₂ /DLC coating on the surface of the substrate.

7 . The preparation method according to claim 6 , wherein the parameters of the base body and the support in step S4 are: base body bias voltage -100～-300V, support rotation at 3rpm/min, revolution at 2～5rpm/min, setting The deposition temperature was 300°C.

8 . The preparation method according to claim 6 , wherein the power supply parameters in step S4 are: frequency 40 kHz, power 3-4 kW, and the duty ratio of the TiB ₂ ceramic target pulse power supply is 25-75%. 9 .

9 . The preparation method according to claim 6 , wherein the distance between the target and the substrate in step S4 is 6-10 cm. 10 .

10. Application of the self-lubricating titanium diboride/diamond-like carbon coating of claims 1-5 in the field of surface protection of cutting tools, molds or mechanical parts.