Summary of the invention
The object of the present invention is to provide a kind of amorphous carbon coating;
Another object of the present invention is to provide the preparation method of above-mentioned coating, and this method is suitable for large-scale production, is used for the structure gradient variation amorphous carbon coating preparation that special easy-abrasion part antifriction is lengthened the life, and has the advantages that the time is short, efficient is high, cost is low.
The invention still further relates to the application that the reparation of using above-mentioned amorphous carbon coating to be used for engine valve tappet, adjustment dish is lengthened the life.
For achieving the above object, the present invention takes following design:
A kind of amorphous carbon coating, it is located on the matrix surface of part, for example, be arranged on the metal surface of parts, this coating comprises metal Ti and Cr by comprising prime coat, intermediate layer and top layer from inside to outside in the prime coat, intermediate layer comprises Ti, Cr and C element, and be the mixed layer of constituent content graded, realize the transition of bottom simple metal layer to the top layer diamond-like coating, top layer is to comprise the diamond-like coating that is doped with little metal Ti and Cr; Wherein, the content of the Cr element in the intermediate layer is the trend of successively decreasing gradually from bottom to the top layer direction, and the C element is the trend that increases gradually, and the content kept stable of Ti element.
One deck Ti and the Cr described prime coat as metal is arranged between matrix and amorphous carbon coating, wherein the atomic percentage conc of Ti and Cr is respectively 5~10% and 40~60%, other is a matrix, and underlying metal and matrix element counterdiffusion mutually, forms the good binding layer; Between described prime coat and the top layer is the intermediate layer that mixes of Ti, Cr and C, and from inside to outside, wherein Cr content is decremented to 20~30% by 40~60%, and the Ti element is stabilized in 5~10%, and the C element is incremented to 60~70% by 30~40%; Described top layer is the amorphous carbon coating of a small amount of Ti of doping, Cr element, and the Ti of doping, Cr atomic percentage conc are 5~10% and 5~20% respectively, and the C constituent content is 70~90%.Usually, the gross thickness of described coating is in the scope of 1.0~3.0 μ m.
The thickness of above-mentioned prime coat metal can be 200~500nm, and the thickness of intermediate layer can be 1000~2000nm, and the thickness of top layer can be 200~500nm.
In the technique scheme of the present invention, bottom is a simple metal, be used to increase the adhesion of coating and matrix material, intermediate layer is the mixed layer of Ti, Cr and C element graded, realize the buffering of bottom simple metal to the top layer diamond-like coating, increase adhesive force of coatings, reduce the internal stress of coating.Top layer is the oligometallic diamond-like coating that mixes, and coating has kept higher hardness and good wear-resisting and antifriction performance.
The preparation technology of above-mentioned amorphous carbon coating is:
Adopt the multi-source magnetron sputtering method, used sputter target material is technical pure chromium Cr target, titanium Ti target and graphite C target, places each two pairs of pure chromium Cr target, titanium Ti target and carbon C targets respectively on the target source position, totally 6 pairs, 12 sputtering targets are controlled the size of the power and the electric current of 6 pairs of sputtering targets by 6 switches; The base vacuum of system begins promptly that the pressure of working space is before this technological process: 1.0~2.0 * 10
-2Pa, operating air pressure is: 2~4 * 10
-1Pa; Keep this operating pressure by feeding working gas for high-purity Ar gas; Preparation section comprises: preparation metal prime coat: open chromium Cr target, titanium Ti target, at substrate surface plated metal prime coat; Preparation splash coating: thereafter, open chromium Cr target, titanium Ti target and graphite C target, carry out the preparation of splash coating, in sputter amorphous carbon coating layer preparation process, feed assisted reaction gas acetylene C
2H
2
The commercially pure degree of each sputtering target is respectively: chromium target purity 99.99%, titanium target 99.8%, graphite target 99.99%.
The purity of working gas high-purity Ar gas is 99.999%, the purity of acetylene gas〉98%.
Its preparation technology parameter can be:
In sputter amorphous carbon coating preparation process, the electric current of Cr target is decremented to 0.2~1.0A successively by 25.0~28.0A, and power is decremented to 1.0~1.5KW successively by 15.0~16.0KW; The electric current of Ti target is decremented to 5.0~7.0A successively by 30.0~35.0A, and power is decremented to 5.0~6.0KW successively by 17.0~17.5KW; The graphite C target current is incremented to 21.0~25.5A successively by 0.5~2.0A, and power is incremented to 15.0~16.0KW successively by 1.0~1.5KW.On workpiece, form thus by intermediate layer and top layer at interior whole amorphous carbon coating.In preparation intermediate layer and top layer process, pulsed bias also is set, from-600~-400V is initial, successively decreases gradually, and the end of a period bias voltage is not less than-50V, and dutycycle is incremented to 80% by 60%.
Concrete, the preparation process of coating mainly can comprise five steps: vacuumize; Sputter clean; Main bombardment bottoming; Plated film; Cooling.
1. vacuumize:
Make the pressure of working space reach the described pressure that background requires,
Time for roughing 5~10min is evacuated to 2.0~2.6 * 10
0Pa;
45~the 60min that carefully finds time is evacuated to 1.0~2.0 * 10
-2Pa.
2. sputter clean:
Before deposited coatings, with high-energy argon ion surface of the work is bombarded purification, remove foreign atom, improve adhesive force of coatings, the pulsed bias that can select for use-1400~-1200V, dutycycle 70%, argon flow amount 220~230sccm, the time is 10~15min.
3. main bombardment bottoming:
At substrate surface plated metal prime coat, the technological parameter of sputtering target is as shown in table 1.
The technological parameter of sputtering target during table 1 bottoming
Other parameter: pulsed bias-800~-600V; Dutycycle 50%; Argon flow amount 50~60sccm; Time 10min;
4. during plated film:
The technological parameter of sputtering target is as shown in table 2 when (1) depositing intermediate layer.
Be to improve deposition efficiency and bond strength, can add pulsed negative bias during plated film: by-600~-400V, according to per 10~15min of the time interval successively decrease-100V is till-the 100V, corresponding, dutycycle increases by 5% until 80% by 60% every 10min; Argon flow amount 50~60sccm, acetylene flow 5sccm.
The power of chromium target and titanium target reduced by 2~3KW in per 10~15 minutes, and electric current reduced by 3~5A in per 10~15 minutes; The power of graphite target increased by 2~3KW in per 10~15 minutes, and electric current increased by 3~5A in per 10~15 minutes.Sedimentation time is 60min.
The technological parameter of sputtering target during table 2 deposition intermediate layer
(2) technological parameter of sputtering target is as shown in table 3 during deposited top layer DLC.
The technological parameter of sputtering target during table 3 deposited top layer DLC
Be to improve deposition efficiency, can add during plated film pulsed negative bias-150~-50V, dutycycle 80%.Argon flow amount 50~60sccm, acetylene flow 5sccm.
The power of chromium target and titanium target reduced by 2~3KW in per 10~15 minutes, and electric current reduced by 3~5A in per 10~15 minutes; The power of graphite target increased by 2~3KW in per 10~15 minutes, and electric current increased by 3~5A in per 10~15 minutes.Sedimentation time is 20min.
The thickness of the amorphous carbon coating of the graded that finally obtains is at 1.0~3.0 μ m.
5. cooling:
When charging into argon gas 220sccm assistant coating cooling 30~40min to the 80 ℃ of left and right sides, close argon gas, in reacting furnace, charge into air and be cooled to room temperature.
In above-mentioned technological process, feeding argon gas mainly is in order to carry out sputter and to keep vacuum;
Acetylene flow when deposited coatings (transition zone and top layer) is 5sccm always.
Preparation graded coating at first deposits chromium Cr and the bottoming of titanium Ti metal level as prime coat among the present invention, and deposition contains the gradient layer of metallic element and carbon then.
In this coating preparation process, but aerobic sneak into, cause also containing a spot of oxygen element impurity, do not wait at different layer content, about 10%.Its performance and preparation influence to coating is little.The amount that therefore, in the data of the element atomic percentage conc of aforementioned each layer coating, also should comprise oxygen element impurity.
The graded amorphous carbon coating of the present invention preparation has that hardness height, friction factor are low, self-lubricating property and wear resistance is good and advantage such as coating surface good quality.Adopt this technology prepare coating have the time short, efficient is high, cost is low, be suitable for large-scale production, be used for special easy-abrasion part antifriction lengthens the life, this coating has good abrasion resistance and antifriction performance under higher contact stress effect; Simultaneously, coating and steel as matrix material have bond strength preferably.Therefore has bigger using value.
The reparation that this special construction coating can be used as the Diesel engine critical component is lengthened the life and modified coating, especially the new coating that the reparation of engine valve tappet, adjustment dish is lengthened the life, but such slip under severe rugged environment of significant prolongation and the life-span of load bearing element.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
According to the real material of the valve tappet of automobile engine, as the base material sample, used depositing device is a DM205013 multi-source magnetic control sputtering device with the monocrystalline silicon Si (N-100 type) of 20Cr, Cr12W and single-sided polishing.
Embodiment 1:
As shown in Figure 1, 2, adopt the multi-source magnetron sputtering method, a pivoted frame 0 is set in sputtering equipment, workpiece 1 is set on pivoted frame 0, promptly prepare the monocrystalline silicon piece workpiece 1 of φ 125mm single-sided polishing.This pivoted frame 0 rotates around it central shaft 01 and rotates, on and two circumference that spacing equates concentric inboard pivoted frame 02 and outside fixed mount 03 are set at the inside and outside and pivoted frame 0 of this pivoted frame 0, on inboard pivoted frame 02 and outside fixed mount 03 pivoted frame fixing target source position socket is set, on the target position socket sputtering target is set, the sputtering target of circle rotates on the inboard pivoted frame 02, the sputtering target of circle is fixed on the fixed mount 03 of the outside, and carbon target 3, chromium target 2 and titanium target 4 are set respectively on the Internal and external cycle target position of inboard pivoted frame 02 and outside fixed mount 03.As shown in Figure 1, on the target source position of inboard pivoted frame 02 and outside fixed mount 03, place each two pairs of pure chromium Cr target, titanium Ti target and carbon C targets respectively, totally 6 pairs, 12 sputtering targets, each is in the sputtering target, and one is arranged on the inboard pivoted frame 02 inner ring pivoted frame, one is arranged on the fixed mount 03 outer ring pivoted frame of the outside, controls the size of the power and the target stream of 6 pairs of sputtering targets by 6 switches; The sputtering target revolution of inboard pivoted frame 02 inner ring is promptly rotated around central shaft 01, and the sputtering target of outer ring is fixed.The correspondence position of each target just immobilizes according to shown in Figure 1.Position and accompanying Fig. 1 position consistency of the sputtering target reality when the preparation coating, each is separately positioned on two concentric circumferences target holders two in the target, is alternately equally distributed substantially.Distributing order is: Cr, C, Ti, Ti, C, Cr, workpiece 1 place on the workpiece pivoted frame of centre of two concentric circles target holders.The distance of inboard each target is even, the close together of outside C target and Ti target.With sputter target material is technical pure chromium Cr target, titanium Ti target and graphite C target, commercially pure degree: chromium target purity 99.99%, titanium target 99.8%, graphite target 99.99%.
Workpiece is fixed on the pivoted frame and only revolves round the sun, self not rotation.Workpiece is fixed on the swivel mount apart from the target surface appropriate position, and promptly workpiece generally is fixed in the centre position of pivoted frame, this position deposition efficiency height.Distance between the distance of sputtering target and pivoted frame and each target is fixed in this existing equipment, need not adjust.Pivoted frame 0 rotary speed is 4r/min (being workpiece revolution rotating speed), and carbon target, chromium target and titanium target are with the speed different with workpiece (about 10r/min), and turn to and the turning in the same manner of inboard sputtering target of workpiece are rotated.During deposited coatings, by control electric current of sputtering target and the duty that power is controlled target, the debugging power of target just quits work during to minimum of a value.Control the size and the distribution situation of the content of element in the coating by the size of control electric current of sputtering target and power.
Working gas is a high-purity Ar gas, and assisted reaction gas acetylene is C
2H
2(purity〉98%), the base vacuum of system begin promptly that the pressure of working space is before this technological process: 1.0~2.0 * 10
-2Pa, operating air pressure is: 2~4 * 10
-1Pa.
Its preparation technology parameter can be: the electric current of Cr target is decremented to 0.2~1.0A successively by 25.0~28.0A, and power is decremented to 1.0~1.5KW successively by 15.0~16.0KW; The electric current of Ti target is decremented to 5.0~7.0A successively by 30.0~35.0, and power is decremented to 5.0~6.0KW successively by 17.0~17.5KW; The graphite C target current is incremented to 21.0~25.5A successively by 0.5~2.0A, and power is incremented to 15.0~16.0KW successively by 1.0~1.5KW.On workpiece, form thus by intermediate layer and top layer in interior whole coating.Its technology can comprise and vacuumizing; Sputter clean; Main bombardment bottoming; Plated film; Cool off five operations;
At first, slightly vacuumize, be evacuated to 2.0~2.6 * 10
0Pa; Carefully vacuumize again.By slightly taking out and carefully vacuumizing, make reative cell extracting vacuum to 1.6 * 10
-2Pa, time 52min;
Use argon gas (purity is 99.999%) that surface of the work is carried out sputter clean 10min then, remove foreign atom, select pulsed bias-1300V for use, dutycycle 70%, argon flow amount 220sccm;
Then begin to lead bombardment bottoming and form prime coat, the power of chromium target and titanium target is respectively 15.0 and 17.0KW, and electric current is respectively 26.0 and 28.5A, bottoming process time 10min;
Also can put pulsed bias-700V; Dutycycle 50%; Argon flow amount 50~60sccm.
Begin plated film then, deposit the intermediate layer coating earlier, the power of chromium target, titanium target is begun by 15KW and 17KW respectively, average every 10min 2KW that successively decreases, and electric current is begun by 25.3A and 30.7A respectively, average every 10min 3.5A that successively decreases, the power of carbon target is begun by 1KW simultaneously, and average every 10min increases progressively 2KW, and electric current is begun by 1.6A, average every 10min increases progressively 3.2A, and the time is 60min;
Be to improve deposition efficiency and bond strength, add pulsed negative bias during plated film: by-500V, according to per 10~15min of the time interval successively decrease-100V is till-the 100V, corresponding dutycycle increases by 5% until 80% by 60% every 10min; Argon flow amount 50~60sccm, acetylene flow 5sccm.
And then begin deposited top layer,
The power of chromium target, titanium target and graphite target is respectively from 5.0KW, 5.0KW and 11.0KW, electric current respectively from 8.4A, 14.4A and 18.0A begin with the identical rate variation of deposition intermediate layer, time 20min.Acetylene flow 5sccm.
For improving deposition efficiency, add pulsed negative bias-100V during plated film, dutycycle 80%.
At last, cooling:
When charging into argon gas 220sccm assistant coating cooling 30~40min to the 80 ℃ of left and right sides, close argon gas, in reacting furnace, charge into air coating is cooled to room temperature.The thickness of the coating that makes is 1.49 μ m.The thickness of each layer is: the thickness of prime coat metal is about 250nm, and the thickness of intermediate layer is about 1040nm, and the thickness of top layer is about 200nm.
Utilize the multifunctional nano tester to record the nanometer dynamic performance of graded amorphous carbon coating.The result shows that coating has higher nano hardness and elastic modelling quantity, the highlyest can reach 12GPa and 190GPa respectively.
Use Quanta 200 environmental scanning electron microscopes (Dutch Philips company) in conjunction with Genesis energy disperse spectroscopy (U.S. EDAX company) to the coating section structure with element distributes and composition is analyzed.From the energy-spectrum scanning result of Fig. 3 as can be seen, there are clearly C peak, Cr peak and Ti peak.The atomic percentage conc of C reaches 71.34%, and the atomic percentage conc of Cr and Ti is respectively 20.14% and 4.88%, illustrates that the composition in the coating mainly is a carbon, a spot of Metal Cr of mixing in addition and Ti element.As can be seen from Figure 4, the coating densification of graded amorphous carbon coating combines well with basal body interface.Metal Cr, Ti element gradually change to coating surface content from ground, and wherein, Metal Cr, Ti element increase then gradually earlier and reduce, and C content increases gradually.Metallic element in the coating can effectively reduce the internal stress of coating, improves Bond Strength of Coating.Three kinds of coating surface roughness are suitable substantially, and all in 8~10nm nanometer scale, coating surface is very uniform and smooth.
Adopt distribution and the atomic percentage conc of PHI-700 nanometer Auger scanning system (Japanese UL VAC-PHI company) testing coating, as shown in Figure 5 along the cross-wise direction element.Experiment condition: adopt coaxial electron gun and CMA energy analyzer, the electron gun high pressure is 5KV, and energy resolution is 1 ‰, and incidence angle is 30 °, and it is 3.9 * 10 that analysis room's vacuum is better than
-9Torr.Sputtering condition: sweep type Ar+ rifle, energy are 2.0KV, and area is 2 * 2mm
2, sputter rate is about 90nm/min; Standard specimen is thermal oxide SiO
2/ Si.As can be seen from Figure 5, coating is significantly distinguished three zones: prime coat, intermediate layer and top layer.Prime coat mainly is a metallic element, contain 52% Cr element, 6% Ti element and a spot of C, Si element, and the content of metallic element increases gradually to the top layer direction from prime coat; Transition zone mainly is C, Cr, Ti element, and wherein the content of Metal Cr element is decremented to 23% gradually from 52%, and the content of C element increases to 65% gradually from 26%, and the content of Ti element is 9%; Top layer mainly is the amorphous carbon coating, and the content of C element reaches 76%, contains a spot of Metal Cr, Ti element simultaneously, and content is respectively 7% and 11%.During the Auger test, also contain a spot of oxygen element impurity among the result of test, do not wait at different layer content, about 10%.Oxygen mainly prepares and sneaks into when testing, and is little to the performance and the preparation influence of coating.Because main what consider is the variation of metallic element and carbon, so the figure line of oxygen is not showed among Fig. 5.Utilize the micro-friction testing instrument of CETR to record the friction factor of coating under DRY SLIDING.From the friction factor change curve of Fig. 6 as can be seen, under the experimental condition of load 2.0N, rotating speed 250r/min, time 40min, friction factor when uncoated silicon wafer-based soma rubs is about 0.4, and the fluctuation of friction factor is comparatively obvious in the process of friction, and the friction factor when depositing the silicon chip dry friction of amorphous carbon coating remains on about 0.1 substantially, the fluctuation of curve is very little, changes very steady.Adopt the polishing scratch contour curve on TR240 surface roughometer test sample surface, calculate the wear volume loss and the wear rate of coating according to the trough on the curve.By calculating, obtain the coating polishing scratch wear volume and wear rate be respectively 8.33 * 10
3Mm
3With 5.0 * 10
-9Mm
3/ N.m.In addition, in the friction environment of oil lubrication, the friction factor of coating is stabilized in about 0.08 under the identical experimental condition, and the curve fluctuation is very little; The wear rate of coating has been difficult to record.Uncoated friction test is dry friction.Because actual condition has oil lubrication, so on the basis of plated film and plated film frictional behaviour comparison, the friction test with dry friction and oil lubrication compares again, investigates the friction and wear behavior of coating under different operating modes.
With above-mentioned amorphous carbon coating, be used for the Diesel engine tappet, the reparation of adjustment dish is lengthened the life.
Tappet material in the high-horsepower diesel engine match mechanism is Cr12W, and matrix is through the temper of quenching, and more than the matrix hardness HRC43, working face nitrogen treatment, infiltration layer are controlled at 0.01~0.015 μ m, more than the hardness 800HV.Higher matrix hardness adds the performance requirement that case hardness and wear-resisting nitration case could satisfy part, but it is not still very reliable at work, sometimes occur than wiping, peel off, spot corrosion etc., extensively adopted soldering hard metal tip or potsherd to come replaced C r12W nitrogen treatment at present abroad.In order to reduce production costs, the invention provides the described amorphous carbon coating of sputter on the Cr12W matrix, can also use 20Cr to do matrix, carburizing and quenching guarantees its hardness greater than 700HV, and the amorphous carbon coating that changes at the matrix surface sedimentation gradient satisfies the performance requirements such as hardness, wearability of part then.
Embodiment 2
Adopt the technology identical on silicon chip, 20Cr and Cr12W test button, to prepare first group of coating with embodiment 1.By changing the transformation period of sputtering target power and electric current, second group of coating of preparation on monocrystalline silicon piece.The power of chromium target and titanium target is respectively 15.1KW and 17.0KW during bottoming, and electric current is respectively 26.8A and 28.8A, time 10min; During deposited coatings, the power of chromium target, titanium target is begun by 15KW and 17KW respectively, average every 15min 3KW that successively decreases, electric current is begun by 26.9A, 30.6A respectively, average every 15min 5.3A that successively decreases, and the power of carbon target is begun by 1KW simultaneously, average every 15min increases progressively 3KW, electric current is begun by 1.2A, and average every 15min increases progressively 5A, and sedimentation time is 60min; The power of chromium target, titanium target and graphite target is respectively from 6.1KW, 6.0KW and 9.1KW during deposited top layer, electric current is respectively from 11.0A, 12.4A and 15.9A, with with deposition intermediate layer identical rate variation, time 20min, other sedimentary condition is identical with embodiment 1.The constituent content that obtains each layer of coating is similar to embodiment, and the thickness of each layer is for being approximately, and the thickness of prime coat metal is about 300nm, and the thickness of intermediate layer is about 1500nm, and the thickness of top layer is about 300nm.Gross thickness is about 2.1 μ m.
Adopt identical method of testing that the friction and wear behavior and the mechanical property of coating are tested.Frictional behaviour experimental condition: load 5.0N, rotating speed 500r/min, time 60min.The friction factor of coating is shown in Fig. 7 a and 7b.The friction and wear behavior of coating and Mechanics Performance Testing result are as shown in table 4.Under the condition of oil lubrication, the wear rate of coating is very low, adopts TR240 type surface roughometer to be difficult to the polishing scratch of coating is tested.As can be seen from Table 4, the nano hardness and the elastic modelling quantity of coating are higher, and friction factor and wear rate are lower, meet design requirement.
Table 4 deposits the mechanical property and the friction and wear behavior of silicon chip, 20Cr sample and the Cr12W sample of amorphous carbon coating
Embodiment 3
By changing the transformation period of sputtering target power and electric current, prepare another group coating.The power of chromium target and titanium target is respectively 15.0KW and 17.1KW during bottoming, and electric current is respectively 25.6A and 27.8A, time 10min; During deposited coatings, the power of chromium target, titanium target is begun by 15KW and 17KW respectively, average every 5min 1KW that successively decreases, electric current is begun by 26.8A and 30.4A, average every 5min 2A that successively decreases, the power of carbon target is begun by 1KW simultaneously, average every 5min increases progressively 1KW, electric current is begun by 1.7A, average every 5min increases progressively 2A, and sedimentation time is 60min, and the power of chromium target, titanium target and graphite target is respectively from 4.0KW, 6.0KW and 12.1KW during deposited top layer, electric current respectively from 7.8A, 13.5A and 21.4A with identical rate variation, time 20min.Argon flow amount 50~60sccm, acetylene flow 5sccm.(no longer reducing with regard to keeping this value when the electric current on the sputtering target is reduced to the 1A left and right sides) if too low meeting causes the pollution of this target
The performance of prepared coating (load is 0.5N during frictional wear experiment, and other condition is with embodiment 1) as shown in table 5.As can be seen from Table 5, the hardness of coating is lower, and friction factor is higher, can not meet design requirement.
The mechanical property of table 5 coating and friction and wear behavior
By embodiment 1,2,3 as can be seen, on the sputtering time of intermediate layer and top layer, keep 10~15min increasing or decreasing relevant parameter at interval, the coating performance that obtains is better, and too short at interval, then coating performance is bad, and it is long at interval, coating performance neither be fine, therefore, and overlong time or too shortly all can influence performance.