CN1065925C

CN1065925C - Low-temp. method and device for preparation of large area eka-diamond carbon film

Info

Publication number: CN1065925C
Application number: CN97103251A
Authority: CN
Inventors: 夏立芳; 孙明仁; 马欣新; 孙跃
Original assignee: Harbin Institute of Technology
Current assignee: Harbin Institute of Technology
Priority date: 1997-04-17
Filing date: 1997-04-17
Publication date: 2001-05-16
Anticipated expiration: 2017-04-17
Also published as: CN1196401A

Abstract

The present invention provides a method and device for preparing diamond-like carbon film with large area on the surface of a material at a low temperature. More specifically, carbonaceous gases are filled into a sealed vacuum chamber, high negative voltage pulse is applied to a workpiece, plasma is excited, and a large area diamond-like carbon film with no interface among film bases is formed on the surface of the workpiece under the condition of unchanged workpiece temperature. The device is a vacuum chamber with a sealed magnetic field, a high voltage pulse power supply and a magnetic field are arranged outside the vacuum chamber, and a working table or a bracket, a high voltage introducing electrode and an oil cooling and water cooling system are arranged in the vacuum chamber. The method and device can be used for preparing high binding power diamond-like carbon films with no interface on the surfaces of batch workpieces.

Description

Large area eka-diamond carbon film low temperature preparation method and device

The present invention proposes a kind of method and device at material surface deposit one deck diamond-like carbon film.

The preparation method of existing diamond-like carbon (DLC) film has following several, 1. ion beam deposition, 2. ion beam assisted deposition, 3. radiofrequency sputter deposition, 4. magnetron sputtering deposit, 5. vacuum cathode arc deposit, 6. direct current glow discharge deposit, 7. the radio frequency aura is put deposit and laser-(produced)plasma deposit.But these methods all receive certain limitation.Ion beam deposition and ion beam assisted deposition, though can keep workpiece to obtain the DLC film of good combination power at a lower temperature, it be a line-of-sight process, only is applicable to plate part, and non-flat template workpiece surface is difficult to obtain uniform DLC film.Though back several method does not have line-of-sight process, the DLC film that they produce is pure illuvium, and tangible interface is arranged between the film base, and film-substrate cohesion is very poor, and in order to improve film-substrate cohesion, the general requirement base material is heated to about 500 ℃.The technology that has itself requires temperature more than 500 ℃, thereby to rolling bearing class part, and its final thermal treatment temp is lower than 200 ℃ workpiece and can not adopts.

The objective of the invention is to propose low temperature preparation method and device a kind of practicality, large area eka-diamond carbon (DLC) film, on the metal of different shape, nonmetal, ceramic, polymer and semiconductor material product surface, be not higher than under 150 ℃ of conditions in room temperature or base material temperature, obtaining does not have the bonding force at interface good with base material, thickness is from the diamond-like carbon film of nm to μ m magnitude, to improve its hardness, wear resistance, solidity to corrosion, reduction frictional coefficient, and obtain various special physics, chemical property.

The objective of the invention is to realize to have a back of the body end vacuum 1 * 10 what be placed with the above-mentioned materials workpiece by following method and apparatus ^-4In the vacuum chamber of Pa, fill with methane gas or acetylene gas to air pressure 7～1 * 10 ^-1Pa is a negative electrode with the workpiece that is placed on the worktable, and vacuum-chamber wall is an anode, apply 2～30KV pulsed voltage, pulsing glow discharge, methane decomposition gas or acetylene gas, produce carbon-containing plasma, wherein contain carbon ion under electric field action, rush at workpiece surface, part is injected workpiece surface, the part carbon deposition is at workpiece surface, multiple pulses repeatedly repeats this effect, finally forms diamond-like carbon (DLC) film at no interface at workpiece surface.The present invention produces the method for carbon-containing plasma, is mainly the subatmospheric carbonaceous gas under the high voltage pulse effect, and glow discharge takes place.The carbonaceous gas that adopts is generally methane gas or acetylene gas, also can adopt the Volatile Gas of organic liquid, as benzene, acetone etc.Air pressure is generally 7～1 * 10 ^-1Pa.The high voltage pulse that is adopted is: crest voltage 2～30KV, pulsewidth 10～200 μ s, repetition rate: 50～400Hz.

Realize that device of the present invention is an airtight vacuum chamber, highest attainable vacuum is 1 * 10 ^-4Pa, its structure and work synoptic diagram such as Fig. 1. vacuum-chamber wall water cooling, worktable are used by cooling, and worktable can revolve round the sun and rotation.The pulsed voltage, pulsewidth, the repetition rate that produce glow discharge are adjustable continuously, and pulse can apply continuously, also can intermittently apply.Pulsed voltage, pulsewidth, frequency and apply mode, according to workpiece size, quantity, arrange, thickness and workpiece allow working temperature and decide.Apparatus of the present invention mainly comprise vacuum chamber, the magnetic confining field that produces with permanent magnetism or electromagnetism around the vacuum chamber, high-voltage pulse power source, vacuum system and airing system, the cooling system of vacuum-chamber wall and worktable, and the revolution rotation transmission system of worktable, wherein around vacuum chamber 7, constitute magnetic confining field with permanent magnetic strip or solenoid, workpiece 5 is installed on the support 3, support 3 is connected with high voltage electrode 2 insulation and with the outer high-voltage pulse power source 1 of vacuum chamber with vacuum-chamber wall, vacuum system is by bleeding point 6 and vacuum chamber, work support 3 can revolve round the sun, rotation, just change, counter-rotating, and cool off with transformer oil, the vacuum-chamber wall water cooling, vacuum chamber 7 is made by austenitic stainless steel, airing system is communicated with vacuum chamber 7 by inlet mouth 8, the vacuum chamber shape can be a drum shape, square, can be horizontal or vertical, magnetic confining field is used permanent magnet south all around, the arctic is alternately in the vacuum chamber outside, make the cusped magnetic field formation of true chamber interior walls bump the field along the sealing of locular wall, or use magneticfield coil, its row's example makes in the vacuum chamber and produces magnetic confining field along inwall.

The aerospacecraft part that the present invention can be used for various precision drive wearing pieces, particularly work under space environment is made solid lubricant film and wearing layer; the cutting tool of various difficult-to-machine materials, computer magneticmedium protective membrane; as antifriction, wear-resistant protection film, the electrical insulating film on surfaces such as hard disc of computer, magnetic head, optical protection layer etc.The inner and outer ring raceway and the steel ball of bearing steel GCr15 system rolling bearing utilize the present invention, and at each one deck diamond-like carbon film of surface preparation, bonding force is fine, and substrate performance is constant, and frictional coefficient is reduced to below 0.15 surface hardness H by 0.75 _kBe 11～13GPa, wear resistance improves more than 10 times.Titanium alloy T C ₄Carry out plasma based ion earlier and inject N, prepare one deck DLC film on the surface with the present invention again, its frictional coefficient is reduced to below 0.15 by 0.45, and wear resistance improves more than 20 times.With super-hard high-speed steel system gear wheel shaving toothed tool, behind the multi-arc ion coating TiN of footpath, footpath 30KV again, C ₂H ₂After the medium pulse glow discharge was produced the DLC layer, during shaving, heat in metal cutting reduced, and is improved by terraced gear surface roughness, and gear shaver improves more than 3 times work-ing life.Harmonic gear flexbile gear flexible bearing is produced the DLC film with the glow discharge of 20KV pulsed voltage, both made solid lubricant, make wearing layer again, DLC film and the base material produced do not have the interface, film-substrate cohesion is good, thereby in the geartransmission process, flexbile gear and the repeatedly reversed bending distortion of flexible bearing footpath do not take place but the DLC film has peeling phenomenon.

Fig. 1 is an apparatus structure synoptic diagram of the present invention

Fig. 2 is an embodiment of the invention X linear light electronic spectrum composition depth profile

Fig. 3 is embodiment of the invention laser Raman spectrum figure

Fig. 4 is the The friction coefficient friction revolution change curve without the bearing steel GCr15 of surface deposition DLC of the present invention

Fig. 5 is embodiment of the invention The friction coefficient friction revolution change curve

Embodiment 1. bearing steel GCr15 make rolling bearing, make medium with acetylene gas, and air pressure is 4 * 10 ^-1Pa, at pulsed voltage 20KV, under pulsewidth 20 μ s and the repetition rate 60Hz condition, glow discharge continues 2h, produces the DLC film, carries out composition depth analysis result such as Fig. 2 with X linear light Electron Energy Disperse Spectroscopy, as seen there is not the interface between the film base, do not have the composition sudden change, be determined as the DLC film through laser Raman spectrum, as Fig. 3.Frictional coefficient change curve such as Fig. 4 that the GCr15 friction pair of DLC and no DLC is arranged, its wear resistance improves more than 10 times, and contact fatigue life improves more than 10 times.

Embodiment 2. super-hard high-speed steel W6Mo5Cr4V2Al2 make gear wheel shaving toothed tool, and medium is made with acetylene gas then through multi-arc ion coating TiN 2 μ m in the surface, and air pressure is 2 * 10 ^-1Pa is 30KV in pulsed voltage, pulsewidth 30 μ s, and repetition rate is under the 60Hz condition, and pulse glow discharge continues 3h, produces one deck DLC film on the surface, and the working durability is improved 3-5 doubly.

Embodiment 3.TC ₄Titanium alloy injects N through plasma based ion, and then uses acetylene gas, and air pressure is 5 * 10 ^-1Pa, pulsed voltage 20KV, pulsewidth 20 μ s, under the repetition rate 80Hz condition, glow discharge continues 2h in the arteries and veins, forms one deck DLC on the surface, and its frictional coefficient drops to below 0.15 by 0.45, and wear resistance improves 100 times.

Claims

1, a kind of large area eka-diamond carbon film low temperature preparation method is characterized in that: it is indoor that this method comprises the following steps: that workpiece is placed on the airtight vacuum that is added with magnetic field, and its vacuum tightness is≤1 * 10 ^-4Pa, magnetic field is magnetic confining field, magneticstrength is 1000-3000 Gauss, fill with carbonaceous gas, to air pressure be 7～1 * 10 ^-1Pa, with the workpiece is negative electrode, locular wall is an anode, apply the pulsed voltage of 2～30KV, pulsewidth is 10～200 μ s, and repetition rate 50～400Hz excites glow discharge, produce carbon-containing plasma, can under workpiece temperature is lower than 150 ℃ condition, inject and deposit one deck diamond-like carbon film at workpiece surface.

2, method according to claim 1 is characterized in that: exciting the method for carbon-containing plasma, is that filling with carbonaceous gas in vacuum chamber is 7～1 * 10 at air pressure ^-1Under the Pa condition, excite glow discharge with the high-voltage pulse electricity, its used carbonaceous gas can be methane, acetylene, can be the Volatile Gas of organic liquids such as benzene, acetone also, can be single gas, also can be the gas mixture of carbonaceous gas and hydrogen.

3, method according to claim 1 is characterized in that: described workpiece is the workpiece of metal and alloy, can be single workpiece, also can be workpiece in batch.

4, a kind of device that is used for the described method of claim 1 to 3, comprise vacuum chamber, the magnetic confining field that produces with permanent magnetism or electromagnetism around the vacuum chamber, high-voltage pulse power source, vacuum system and airing system, the cooling system of vacuum-chamber wall and worktable, and the revolution rotation transmission system of worktable, it is characterized in that: constitute magnetic confining field all around at vacuum chamber [7] with permanent magnetic strip or solenoid, workpiece [5] is installed on the support [3], support [3] is connected with high voltage electrode [2] insulation and with the outer high-voltage pulse power source [1] of vacuum chamber with vacuum-chamber wall, and vacuum system is by bleeding point [6] and vacuum chamber, and work support [3] can revolve round the sun, rotation, just change, counter-rotating, and cool off with transformer oil, the vacuum-chamber wall water cooling, vacuum chamber [7] is made by austenitic stainless steel, and airing system is communicated with vacuum chamber [7] by inlet mouth [8].

5, device according to claim 4, it is characterized in that: the vacuum chamber shape can be drum shape, square, can be horizontal or vertical, magnetic confining field uses permanent magnet south, the arctic alternately in the vacuum chamber outside all around, make the magnetic confining field of the cusped magnetic field formation of true chamber interior walls along locular wall, or use magneticfield coil, its row's example makes in the vacuum chamber and produces magnetic confining field along inwall.