CN105908143B - Easy-to-rust metalwork surface DLC film and preparation method thereof - Google Patents

Easy-to-rust metalwork surface DLC film and preparation method thereof Download PDF

Info

Publication number
CN105908143B
CN105908143B CN201610293340.7A CN201610293340A CN105908143B CN 105908143 B CN105908143 B CN 105908143B CN 201610293340 A CN201610293340 A CN 201610293340A CN 105908143 B CN105908143 B CN 105908143B
Authority
CN
China
Prior art keywords
preparation
workpiece
rust
diamond
peak value
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610293340.7A
Other languages
Chinese (zh)
Other versions
CN105908143A (en
Inventor
彭继华
苏东艺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Grandtech Co ltd
South China University of Technology SCUT
Original Assignee
Guangzhou Grandtech Co ltd
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Grandtech Co ltd, South China University of Technology SCUT filed Critical Guangzhou Grandtech Co ltd
Priority to CN201610293340.7A priority Critical patent/CN105908143B/en
Publication of CN105908143A publication Critical patent/CN105908143A/en
Application granted granted Critical
Publication of CN105908143B publication Critical patent/CN105908143B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C14/0605—Carbon
    • 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
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses easy-to-rust metalwork surface DLC films and preparation method thereof.The preparation method is first to remove surface contaminant to pretreatment of metal surface；Then pretreated metal is fixed on work rest, using ion source Bombardment and cleaning sample surfaces；Prepare 0.1 0.5 microns of transition zone；Prepare a C of 13 micron thickness：HDLC layers.The present invention is different from tradition and prepares the preparation of DLC coatings, improve the ionization level of hydrocarbon, reasonably improve substrate temperature, improve the diffusion mobility for adsorbing particle on surface, carbon ion is set to be moved to groove or pit, conducive to fine and close film is generated, even if metal surface is the Non-smooth surface face of wire drawing/sandblasting, the obtained coating of the present invention still has excellent corrosion resisting property and film base adhesive force.

Description

Easy-to-rust metalwork surface DLC film and preparation method thereof
Technical field
The present invention relates to Treatment of Metal Surface, carbon structural steels more particularly to surface Jing Guo wire drawing, blasting treatment and Cast iron part surface DLC film and preparation method thereof so that easy-to-rust metalwork has high corrosion-resistant and high-wearing feature Feature.
Background technology
Carbon structural steels and cast iron materials are widely used in numerous areas, these materials are under clean atmospheric environment Be easy to be corroded, let alone sulfur-bearing, chloride ion-containing harsh environment under work use.The corrosion of material and workpiece causes Huge waste and destruction.It is estimated that almost in All Countries, the loss that metal erosion generates is every year close to state's national product The 5% of total value, it is even more.How to be effectively prevented corrosion of metal becomes the significant problem of global concern.Since recognizing Since electrochemical corrosion is the dominant mechanism of metal erosion, various process for treating surface, such as plating, Brush Plating, chemistry The electrochemical process for treating such as plating, surface passivation become the mainstream technology of easy-to-rust Treatment of Metal Surface.Although above method effect It is good, at low cost, but the environmental pollution effect brought increasingly is amplified, therefore there is an urgent need for the correlation replacement for representative is electroplated Treatment technology.
In certain high added value workpiece products, vapor deposition, including physical vapour deposition (PVD) and chemical vapor deposition surface Treatment technology is expected to replace traditional electroplating technology.Especially golf industry, the high request for material performance itself and reduction Cost angle, more easy-to-rust steel trades mark are applied in bulb manufacture, propose to substitute compeling for traditional electrolyte matter plating in industry Highly necessary ask.It has been obtained at present using rational gas phase deposition technology in carbon steel smooth after a polish, cast iron steel piece surface Good effect, especially a kind of diamond-film-like that high resistance insulating properties is excellent (DLC) occurs and certain suitable treatment technologies The corrosion resistance of these easy-to-rust steel parts is even more increased to the height being electroplated considerably beyond traditional electrolyte matter.
Chinese invention patent CN102498232B discloses the substrate and preparation method thereof of diamond-like rock layers, and this method exists 17Cr3 steel surfaces coat DLC coatings, and use high silicon ingredient close pinhole, can resisting salt fog corrosion be increased to 150 from 30 hours Hour.Chinese invention patent application CN103160794 " in the method that carbon steel or spheroidal graphite cast-iron surface prepare diamond-film-like " The coating that binding force is more than 65N is obtained using high-frequency bipolar pulsed magnetron sputtering.Chinese invention patent application CN103956592A, The high voltage power transmission ground connection net means that CN104726873A is directed to Q235 materials respectively implement NiP-DLC combined processings, to petroleum pipeline Implement carburizing-DLC combined processings with carbon steel parts surface and obtain amazing anti-corrosion effect in road.
But it must be, it is emphasized that the above results and existing literature, which are reported in, discusses that diamond-like coating raising easy-to-rust metal is resistance to When corrosion energy, always using the Specimens of polishing.Specimens are conducive to excellent in surface growth consistency height, continuity Coating, i.e., pinhold density is small in coating, and pinhole size is also small, therefore bright to insulating effect or the resistance effect of oozing for corroding electrolyte It is aobvious, in addition selecting the DLC coatings of high value, block corrosion micro cell, brings apparent anti-corrosion effect.Simultaneously for one 17-4H steel golf club heads with burnishing surface region, wire-drawing surface or sandblasting face region, using the preparation sides DLC traditional at present The preparation method that method or above-mentioned patent CN102498232B are proposed, salt spray corrosion test discovery, wire drawing/sand blasted area and polishing area The great difference of corrosion resistance in domain, spray light region do not occur corrosion spot 150 hours yet, but wire drawing/sand blasted area 12 hours There is corrosion spot afterwards.This phenomenon illustrates that existing DLC prepares treatment technology and is difficult in metal wire-drawing/sand blasted surface life The DLC coatings that long consistency is high, continuity is excellent.Because of existing traditional low temperature DLC preparation methods, no human relations are that physical vapor is heavy Product (PVD) or plasma enhanced chemical vapor deposition (PECVD), the carbon particle of acquisition are in almost straight under biasing electric field effect Line moves, and generates " visual angle " effect, and there is also " point effects " for charged particle, thus the groove of wire drawing/sandblasting, pit must So generate coating defects.
Invention content
The technical problem to be solved by the present invention is to be directed to easy-to-rust metal non-smooth surface to provide such as wire drawing/sandblasting face A kind of acquisition high-bond, high-compactness and high successional anti-corrosion diamond-film-like and preparation method thereof, so that industry is answered With.
The smooth phenomenons of surface irregularities such as the pit of groove, sandblasting generation that the present invention is generated for wire drawing, improve carbon member The film forming components such as element are uniformly distributed ability surface, to form film layer as in homogeneous thickness as possible in all regional areas Covering.It obtains having both high corrosion-resistant and the Non-smooth surface easy-to-rust metal surface vapor deposition protective coating of high film-substrate cohesion
The preparation method of Non-smooth surface easy-to-rust of the present invention metal surface vapor deposition diamond-like protective coating is in workpiece Surface applies bipolar pulse bias, enhances wire drawing groove and sandblasting pit to depositing grain by frequency, the reasonable change of duty ratio The reception absorption of son；Workpiece surface temperature is rationally improved using heating, and improves the ionization level of deposited particles, promotes to receive and adsorb Particle to workpiece surface has high kinetic energy in diffusion into the surface.By the above aggregate measures, obtained in wire drawing/sand blasted surface thick Spend uniform, high-compactness and high successional coating.The needle through coating is avoided as much as using composite layered structure simultaneously Hole defect.
The present invention is in non-smooth surface acquisition high corrosion-resistant, the diamond-like coating of wearability, high-bond.The present invention adopts 850 vacuum coatings of the hauzer flexicoat dress replaced with modulated asymmetric bipolar AC/DC pulse grid bias power supply is configured with (850 types of flexicoat of Dutch HAUZER) is set, which includes vacuum chamber, controlled sputtering source, low-voltage direct The work rest of radiant heating device, asymmetric bipolar AC/DC pulse grid bias power supply and triple rotations in arc ion source, vacuum chamber, Work rest is mounted on internal vacuum chamber；Wherein asymmetric bipolar AC/DC pulse grid bias power supply positive negative pulse stuffing peak value is adjustable, pulse Wave mode is square wave, and the positive negative peak of output voltage is adjustable, and frequency and duty ratio are adjustable.
The object of the invention is achieved through the following technical solutions：
The preparation method of easy-to-rust metalwork surface DLC film, includes the following steps：
1) wire drawing/sandblasting carbon steel metal workpiece surface pretreatment：Remove surface contaminant；
2) pretreated workpiece is fixed on work rest, using ion source Bombardment and cleaning sample surfaces；
3) transition zone is prepared：The argon flow amount for adjusting magnetic control target source, makes pressure in vacuum tank remain 0.5-1Pa；It opens non- Symmetrical bipolar pulsed bias pattern, frequency 300-1000Hz, negative pulse peak value are 50-150V, and positive pulse peak value is 10-20V, Duty ratio is 30-80%；Controlled sputtering source and ion source are opened simultaneously, and magnetic control ource electric current is 20-40A, low-voltage direct arc line For 20-40A；Magnetic control target is closed after the transition zone that workpiece surface prepares 0.1-0.5 microns；
4) diamond-like rock layers are prepared：The positive negative pulse stuffing peak value of asymmetric bipolar pulsed bias is adjusted, negative pulse peak value is 500-1000V, positive pulse peak value are 20-100V, frequency 300-1000Hz, duty ratio 30-80%；It is passed through hydrocarbon Gas, control hydrocarbon gas partial pressure is 0.4-1.0Pa, and a-C is deposited in workpiece surface：H diamond-like coatings.
To further realize the object of the invention, it is preferable that the use ion source Bombardment and cleaning sample surfaces are to close very Empty room door, and start work rest rotation；Vacuum chamber is pumped to back end vacuum and is less than 5x10-3Pa；Open heating device, by matrix plus Heat is to 200-250 DEG C；It is passed through argon gas, it is 0.2-0.3Pa to make pressure in vacuum tank, and argon ion is obtained using low-voltage direct arc ion source Beam Bombardment and cleaning workpiece surface, control beam current are 60-100A, and it is 200-400V that workpiece, which applies Dc bias,；20-30 minutes After close Dc bias.
Preferably, the step 3) transition zone is the metal or alloy for being easily formed carbide.
Preferably, the metal is Ti or Cr.
Preferably, the removal surface contaminant includes that oil removing-rinsing-ultrasonic cleaning-rinsing-acid solution is clear The rinsing of-alkaline solution neutralization-rinsing-deionized water rinsing-preservative is washed, then blows workpiece using oil-free compressed air It is dry.
Preferably, step 3) and bias used in step 4) are the alternating current-direct current biass for having asymmetric bipolar pulse.
Preferably, step 2), step 3) and step 4) are completed at 200 DEG C.
Preferably, the diamond-like coating is the DLC layer of 1-3 micron thickness；Resistance value is more than 100M Ω.
A kind of easy-to-rust metalwork surface DLC film, is made by above-mentioned preparation method；Such thin diamond Film is that transition zone and diamond-like coating obtained form successively on easy-to-rust metalwork surface；Transition region thickness is 0.1- 0.5 micron, diamond-like coating thickness is 1-3 microns.
Compared with the prior art, the advantages of the present invention are as follows：
1) asymmetric bipolar AC power is used when depositing coating of the present invention, is conducive to improve the diffractive of charged particle. Identical as traditional direct current pulse power source depositional model when in negative pulse section, tip is high except negative charge density, the carbon of positive electricity Particle is more attracted at tip；When bias is in positive pulse section, the electronics gathered on surface can be not only neutralized, and same Sample positive charge density at tip is high, there is repulsive interaction, the latter will deviate point under kinetic energy effect positively charged carbon ion End slides to the groove of wire drawing or the place of digging pit of sandblasting, when in window pulse section, theoretically in all areas suction having the same Attached probability.Pass through the variation of the pulse polarity of grid bias power supply so that the chance for receiving absorption deposited particles at groove, peak valley tends to It is impartial.
2) present invention is different from tradition preparation DLC coatings preparation, improves the ionization level of hydrocarbon, reasonably improves Substrate temperature improves the diffusion mobility on surface of absorption particle, is conducive to generate fine and close film, makes carbon ion to groove Or pit movement.
3) coat preparing technology of the invention significantly improves the deficiency of conventional processing technique so that wire drawing/sandblasting gold Metal surface it is processed by the invention after have more excellent anti-corrosion effect and film-substrate cohesion, while also make DLC coatings itself The high-wearing feature possessed is not fully exerted.
Description of the drawings
Fig. 1 is the pulsed bias schematic diagram of the asymmetric bipolar AC/DC pulse grid bias power supply of the embodiment of the present invention 1.
Fig. 2 is the sectional view of 17-4H metal testing plates after embodiment 1 is handled.
It is shown in figure：Workpiece 1, transition zone 2, DLC coatings 3.
Specific implementation mode
To more fully understand the present invention, the present invention is described in detail with reference to the accompanying drawings and examples, but the present invention Embodiment it is unlimited so.
Embodiment 1：The surface treatment of 17-4H metal testing plates
After the 17-4H steel test piece polishing treatments that long generous three-dimensional dimension is 100mmx30mmx2mm, the half of polished surface Wire drawing process is done, is then surface-treated in the following order.
1) test piece of 17-4H steel is dried, dress is hung on fixture, is put into after cleaning line cleaning with oil-free compressed air 850 vacuum coaters of hauzer flexicoat；Wherein magnetic controlled sputtering target is 1 pair of intermediate frequency Cr twin target.Line is cleaned using tool There is the equipment of multi-step multiple-grooved to clean, specifically includes oil removing-rinsing-ultrasonic cleaning-rinsing-acid solution cleaning-alkalinity The cleaning steps such as solution neutralization-rinsing-deionized water rinsing-preservative rinsing.
2) door for vacuum chamber is closed, and starts work rest rotation；Vacuum chamber is pumped to back end vacuum and is less than 5x10-3Pa；It opens 17-4H steel test pieces are heated to 200 DEG C by resistance heating auxiliary device in vacuum chamber.It is passed through argon gas, makes the pressure in vacuum tank be 0.2Pa obtains ar-ion beam Bombardment and cleaning workpiece surface, beam current 100A using low-voltage direct arc ion source, and workpiece is applied It is 200V to add Dc bias；Grid bias power supply is closed after 30 minutes；
3) transition zone is prepared：The argon flow amount for adjusting magnetic control target source, makes pressure in vacuum tank remain 1Pa；It opens asymmetric Bipolar AC/DC pulse grid bias power supply, using asymmetric bipolar pulsed bias pattern (output voltage waveforms are as shown in Figure 1), control Frequency is 1000Hz, and negative pulse peak value is 150V, and positive pulse peak value is 20V, duty ratio 80%；Open controlled sputtering source simultaneously Electric current with low-voltage direct arc ion source, controlled sputtering source is 40A, and low-voltage direct arc ion source line is 40A；Sedimentation time 30 Minute, close magnetic control target after the transition zone that workpiece surface prepares about 0.5 micron.
4) diamond-like rock layers are prepared：The positive negative pulse stuffing peak value of asymmetric bipolar AC/DC pulse grid bias power supply is adjusted, arteries and veins is born It is 1000V to rush peak value, and positive pulse peak value is 100V, frequency 1000Hz, duty ratio 80%；It is passed through methane gas, controls first Alkane partial pressure is 1.0Pa, and the a-C of 3 micron thickness is prepared in workpiece surface:HDLC layers, resistance value is more than 10M Ω.Such as Shown in Fig. 2, after the 17-4H metal testing plates processing obtained by the present embodiment, sequentially formed on the workpiece 1 of 17-4H metal testing plates Layer 2 and DLC coatings 3 are crossed, the thickness of transition zone 2 is 0.5 micron, and 3 thickness of DLC coatings is 3 microns.
Treated, and 17-4H metal testing plates are judged according to DIN CEN/TS 1071-8 standards using 150Kg rockwell indentations DLC coatings reach HF2 grades with basal body binding force, and skin covering of the surface base adhesive force is high.
Processing and untreated 17-4H metal testing plates after GB5938-86 standard salt fog tests according to showing not deal with There is corrosion in 2 hours surfaces of test piece；And processed test piece, either burnishing surface part or drawing portion are passed through 96 hours After salt spray test, not occurring yet can macroscopic rusty stain.
Embodiment 2：The surface treatment of 45A steel test pieces
After the 45A steel test piece polishing treatments that long generous three-dimensional dimension is 100mmx30mmx2mm, the half of polished surface is done Then blasting treatment is surface-treated in the following order.
1) test piece is dried after the cleaning of Special cleaning line with oil-free compressed air, and dress is hung on fixture, is put into hauzer 850 vacuum coaters of flexicoat；Wherein magnetic controlled sputtering target is 1 pair of intermediate frequency Ti twin target.Cleaning line and using has multistep The equipment cleaning of rapid multiple-grooved, specifically includes in oil removing-rinsing-ultrasonic cleaning-rinsing-acid solution cleaning-alkaline solution With the cleaning steps such as-rinsing-deionized water rinsing-preservative rinsing.
2) pretreated workpiece is fixed on work rest, closes door for vacuum chamber, and start work rest rotation；Vacuum chamber It is pumped to back end vacuum and is less than 5x10-3Pa；Resistance assisted heating device in vacuum chamber is opened, 45A steel test pieces are heated to 200 ℃.It is passed through argon gas, it is 0.2Pa to make pressure in vacuum tank, and ar-ion beam Bombardment and cleaning workpiece is obtained using low-voltage direct arc ion source Surface, beam current 60A, it is 200V that workpiece, which applies Dc bias,；Dc bias is closed after 30 minutes；
3) transition zone is prepared：The argon flow amount for adjusting magnetic control target source, makes pressure in vacuum tank remain 0.5Pa；It is non-right to open Claim bipolar AC/DC pulse grid bias power supply, using pulsed bias pattern, output voltage waveforms such as Fig. 1, control frequency is 300Hz, Negative pulse peak value is 50V, and positive pulse peak value is 10V, duty ratio 30%；Simultaneously open controlled sputtering source and low-voltage direct arc from The electric current of component, controlled sputtering source is 20A, and low-voltage direct arc ion source line is 20A；Sedimentation time 10 minutes, in workpiece table Magnetic control target is closed after the transition zone of about 0.1 micron of face preparation.
4) diamond-like rock layers are prepared：The positive negative pulse stuffing peak value of asymmetric bipolar AC/DC pulse grid bias power supply is adjusted, arteries and veins is born It is 500V to rush peak value, and positive pulse peak value is 20V, frequency 300Hz, duty ratio 30%；It is passed through acetylene gas, controls its partial pressure For 0.4Pa, 1 micron of a-C is deposited in workpiece surface：H diamond-like coatings, and its resistance value is more than 40M Ω.
Test piece that treated is according to DIN CEN/TS 1071-8 standards using 150Kg rockwell indentations judgement DLC coatings and base Body binding force reaches HF2 grades, and skin covering of the surface base adhesive force is high.
Processing and untreated test piece are according to showing that the test piece not dealt with 0.5 is small after GB5938-86 standard salt fog tests When surface there is corrosion；And 48 hours salt spray tests are passed through in processed test piece, either burnishing surface part or sandblasting part Afterwards, not occurring yet can macroscopic rusty stain.
The surface treatment of embodiment 3H13 mould steel test pieces
After the H13 steel test piece polishing treatments that long generous three-dimensional dimension is 100mmx30mmx2mm, the half of polished surface is done Then blasting treatment is surface-treated in the following order.
1) test piece is dried after the cleaning of Special cleaning line with oil-free compressed air, and dress is hung on fixture, is put into hauzer 850 vacuum coaters of flexicoat；Wherein magnetic controlled sputtering target is 1 pair of intermediate frequency Cr twin target.Cleaning line and using has multistep The equipment cleaning of rapid multiple-grooved, specifically includes in oil removing-rinsing-ultrasonic cleaning-rinsing-acid solution cleaning-alkaline solution With the cleaning steps such as-rinsing-deionized water rinsing-preservative rinsing.
2) pretreated workpiece is fixed on work rest, closes door for vacuum chamber, and start work rest rotation；Vacuum chamber It is pumped to back end vacuum and is less than 5x10-3Pa；Resistance assisted heating device in vacuum chamber is opened, H13 steel test pieces are heated to 200 ℃.It is passed through argon gas, it is 0.2Pa to make pressure in vacuum tank, and ar-ion beam Bombardment and cleaning workpiece is obtained using low-voltage direct arc ion source Surface, beam current 60A, it is 200V that workpiece, which applies Dc bias,；Dc bias is closed after 30 minutes；
3) transition zone is prepared：The argon flow amount for adjusting magnetic control target source, makes pressure in vacuum tank remain 0.7Pa；It is non-right to open Claim bipolar AC/DC pulse grid bias power supply, using pulsed bias pattern, output voltage waveforms such as Fig. 1, control frequency is 600Hz, Negative pulse peak value is 100V, and positive pulse peak value is 15V, duty ratio 50%；Open controlled sputtering source and low-voltage direct arc simultaneously The electric current of ion source, controlled sputtering source is 30A, and low-voltage direct arc ion source line is 30A；Sedimentation time 20 minutes, in workpiece Magnetic control target is closed after the transition zone of about 0.3 micron of surface preparation.
4) diamond-like rock layers are prepared：The positive negative pulse stuffing peak value of asymmetric bipolar AC/DC pulse grid bias power supply is adjusted, arteries and veins is born It is 800V to rush peak value, and positive pulse peak value is 80V, frequency 600Hz, duty ratio 60%；It is passed through acetylene gas, controls its partial pressure For 0.8Pa, 1 micron of a-C is deposited in workpiece surface：H diamond-like coatings, and its resistance value is more than 50M Ω.
Test piece that treated is according to DIN CEN/TS 1071-8 standards using 150Kg rockwell indentations judgement DLC coatings and base Body binding force reaches HF2 grades, and skin covering of the surface base adhesive force is high.
Processing and untreated test piece after GB5938-86 standard salt fog tests according to showing the test piece not dealt with 1 hour There is corrosion in surface；And 48 hours salt spray tests are passed through in processed test piece, either burnishing surface part or sandblasting part Afterwards, not occurring yet can macroscopic rusty stain.

Claims (10)

1. the preparation method of easy-to-rust metalwork surface DLC film, it is characterised in that include the following steps：
1) wire drawing/sandblasting carbon steel metal workpiece surface pretreatment：Remove surface contaminant；
2) pretreated workpiece is fixed on work rest, using ion source Bombardment and cleaning sample surfaces；
3) transition zone is prepared：The argon flow amount for adjusting magnetic control target source, makes pressure in vacuum tank remain 0.5-1Pa；It opens asymmetric Bipolar pulse bias mode, frequency 300-1000Hz, negative pulse peak value are 50-150V, and positive pulse peak value is 10-20V, duty Than for 30-80%；Controlled sputtering source and ion source are opened simultaneously, and magnetic control ource electric current is 20-40A, and low-voltage direct arc line is 20- 40A；Magnetic control target is closed after the transition zone that workpiece surface prepares 0.1-0.5 microns；
4) diamond-like rock layers are prepared：The positive negative pulse stuffing peak value of asymmetric bipolar pulsed bias is adjusted, negative pulse peak value is 500- 1000V, positive pulse peak value are 20-100V, frequency 300-1000Hz, duty ratio 30-80%；It is passed through hydrocarbon gas Body, control hydrocarbon gas partial pressure is 0.4-1.0Pa, and a-C is deposited in workpiece surface：H diamond-like coatings.
2. preparation method according to claim 1, which is characterized in that described to be using ion source Bombardment and cleaning sample surfaces Door for vacuum chamber is closed, and starts work rest rotation；Vacuum chamber is pumped to back end vacuum and is less than 5 × 10-3 Pa；Open heating dress It sets, matrix is heated to 200-250 DEG C；It is passed through argon gas, it is 0.2-0.3Pa to make pressure in vacuum tank, using low-voltage direct arc ion Source obtains ar-ion beam Bombardment and cleaning workpiece surface, and control beam current is 60-100A, and it is 200- that workpiece, which applies Dc bias, 400V；Dc bias is closed after 20-30 minutes.
3. preparation method according to claim 1, which is characterized in that the step 3) transition zone is to be easily formed carbide Metal or alloy.
4. preparation method according to claim 3, which is characterized in that the metal is Ti or Cr.
5. preparation method according to claim 1, which is characterized in that the removal surface contaminant includes oil removing-drift Washing-ultrasonic cleaning-rinses-acid solution cleaning-alkaline solution neutralization-rinsing-deionized water rinsing-preservative drift It washes, then dries up workpiece using oil-free compressed air.
6. preparation method according to claim 1, which is characterized in that bias used in step 3) and step 4) be have it is non-right Claim the alternating current-direct current bias of bipolar pulse.
7. preparation method according to claim 1, which is characterized in that step 2), step 3) and step 4) are complete at 200 DEG C At.
8. preparation method according to claim 1, which is characterized in that the diamond-like coating is 1-3 micron thickness DLC layer；Resistance value is more than 100M Ω.
9. a kind of easy-to-rust metalwork surface DLC film, which is characterized in that it is by claim 1-8 any one of them Preparation method is made；The DLC film is that transition zone obtained and diamond-like apply successively on easy-to-rust metalwork surface Layer composition.
10. easy-to-rust metalwork according to claim 9 surface DLC film, which is characterized in that the transition zone Thickness is 0.1-0.5 microns, and the diamond-like coating thickness is 1-3 microns.
CN201610293340.7A 2016-05-05 2016-05-05 Easy-to-rust metalwork surface DLC film and preparation method thereof Active CN105908143B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610293340.7A CN105908143B (en) 2016-05-05 2016-05-05 Easy-to-rust metalwork surface DLC film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610293340.7A CN105908143B (en) 2016-05-05 2016-05-05 Easy-to-rust metalwork surface DLC film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105908143A CN105908143A (en) 2016-08-31
CN105908143B true CN105908143B (en) 2018-07-27

Family

ID=56753281

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610293340.7A Active CN105908143B (en) 2016-05-05 2016-05-05 Easy-to-rust metalwork surface DLC film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105908143B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106637128B (en) * 2016-12-08 2019-05-14 华南理工大学 Gold and its alloy surface transparent diamond nano thin-film and preparation method thereof
CN107217228B (en) * 2017-05-18 2019-11-22 清华大学 Improve the method and bearing of bearing wear-resisting property
CN108977766B (en) * 2018-07-18 2020-09-11 南京理工大学 Multilayer composite diamond-like carbon film material and preparation method thereof
CN108977781B (en) * 2018-07-28 2021-06-08 华南理工大学 Method for depositing W-N hard film on surface of hard alloy by magnetron sputtering composite technology
CN109943824B (en) * 2019-04-28 2020-08-18 华南理工大学 Preparation method of high-hardness conductive carbon-based film
CN111424250B (en) * 2020-05-19 2022-02-01 中国科学院兰州化学物理研究所 Preparation method of ultra-lubricity composite nano talcum powder hydrogen-carbon-containing film
CN111455325B (en) * 2020-05-19 2022-02-01 中国科学院兰州化学物理研究所 Method for preparing ultra-smooth hydrogen-carbon-containing film through self-assembly of black phosphorus nanosheets

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0474369A1 (en) * 1990-09-01 1992-03-11 United Kingdom Atomic Energy Authority Diamond-like carbon coatings
CN102673043A (en) * 2012-05-15 2012-09-19 北京有色金属研究总院 Wear-resistant coating with high rigidity and low friction coefficient for textile steel collar and depositing method thereof
CN103952664A (en) * 2014-05-02 2014-07-30 合肥永信信息产业股份有限公司 Surface pretreatment process for diamond-like carbon coated workpiece
CN204840841U (en) * 2015-03-31 2015-12-09 广州今泰科技股份有限公司 Blue ceramic golf push rod

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0474369A1 (en) * 1990-09-01 1992-03-11 United Kingdom Atomic Energy Authority Diamond-like carbon coatings
CN102673043A (en) * 2012-05-15 2012-09-19 北京有色金属研究总院 Wear-resistant coating with high rigidity and low friction coefficient for textile steel collar and depositing method thereof
CN103952664A (en) * 2014-05-02 2014-07-30 合肥永信信息产业股份有限公司 Surface pretreatment process for diamond-like carbon coated workpiece
CN204840841U (en) * 2015-03-31 2015-12-09 广州今泰科技股份有限公司 Blue ceramic golf push rod

Also Published As

Publication number Publication date
CN105908143A (en) 2016-08-31

Similar Documents

Publication Publication Date Title
CN105908143B (en) Easy-to-rust metalwork surface DLC film and preparation method thereof
CN109943824A (en) A kind of preparation method of the carbon-base film of high rigidity conduction
CN102994967B (en) Ultra high speed preparation method for ultra thick diamond-like coating
Wang et al. A novel electrodeposited Ni–P gradient deposit for replacement of conventional hard chromium
CN103233219B (en) Metal TiN ceramic coating preparation process method
CN102728529B (en) Metal alloy imitation hexavalent chromium color high-corrosion-resistant dry surface processing method
CN108977651B (en) Deposition method of high-life composite coating on high-temperature die
CN106191794A (en) The coating method of titanium alloy surface superhard anti-friction wear-resistant composite film and titanium alloy material
CN109208054A (en) A kind of compound coating of resistance to trowel used for plastering of differential arc oxidation and its production method
CN103952671A (en) Multi-arc ion plated hard coating prepared by adopting frequency-modulation electromagnetic coil, and method
CN107338409A (en) Controllable magnetic field arc ion plating prepares the process of nitrogen base hard coat
CN104694926B (en) A kind of process that NiCr wear-resistant coatings are prepared on copper surface
CN106929799B (en) High temperature resistant protective coating and the preparation method and application thereof
CN104746072A (en) Magnesium alloy microarc ion plating surface treatment method
CN104294343A (en) Preparation method of diamond-like composite carburizing layer of steel surface
CN103046073B (en) The novel composite electrode material of a kind of iron-based, copper transition layer and surface nitride coating and preparation method
CN103029370A (en) Iron-based electrode material with pure copper transition layer and surface pure metal molybdenum or tungsten coating and preparation method for electrode material
CN108977781A (en) A kind of method of carbide surface magnetron sputtering complex technique deposition W-N hard films
CN104120377B (en) A kind of method that adopts detonation flame spraying to prepare Al coating on sintered Nd Fe B surface
Shah et al. Influence of substrate temperature on adhesion strength of TiN coating of biomedical Ti–13Zr–13Nb alloy
CN103397328B (en) A kind of absolutely dry method of carrying out high decoration functions composite film coating in metallic surface
CN103628032B (en) A kind of method preparing nano silicon nitride titanium layer in conductive substrate material
CN111020479B (en) High-shielding-piece corrosion-resistant multi-element coating, preparation method thereof and device used by preparation method
CN102367566B (en) Cast iron vacuum chromium plating method
CN110777413B (en) Method for laser remelting of surface of plasma cathode electrolytic deposition ceramic coating

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant