CN107012424A - A kind of TiZrB2Hard coat and its preparation method and application - Google Patents

A kind of TiZrB2Hard coat and its preparation method and application Download PDF

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Publication number
CN107012424A
CN107012424A CN201710141355.6A CN201710141355A CN107012424A CN 107012424 A CN107012424 A CN 107012424A CN 201710141355 A CN201710141355 A CN 201710141355A CN 107012424 A CN107012424 A CN 107012424A
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matrix
tizrb
coating
hard coat
tib
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CN107012424B (en
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代伟
高翔
王启民
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Guangdong University of Technology
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Guangdong University of Technology
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    • 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
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • 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
    • C23C14/22—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
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target

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  • 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 belongs to surface protection technique and related coatings technical field, a kind of TiZrB is disclosed2Hard coat and its preparation method and application.The coating is with TiB2For principal crystalline phase, metal Zr is time crystalline phase, is prepared and synthesized using bipolar pulse magnetron sputtering technique.Wherein TiB2Content is 65~95at.%, and Zr contents are 5~35at.%；The matrix of the coating uses hard alloy, monocrystalline silicon, glass, high-speed steel, steel alloy or titanium alloy, and the thickness of coating is 1.0~1.3 μm.The coating hardness is up to more than 28GPa, and electric conductivity is good, while having good toughness and anticorrosive, Burning corrosion resistance energy and excellent friction, polishing machine, can be widely applied to the fields such as cutter, mould, electrical contact, protection；And this method preparation technology is simple, and with short production cycle, cost is low, is easy to large-scale industrial production.

Description

A kind of TiZrB2Hard coat and its preparation method and application
Technical field
The invention belongs to surface protection technique and related coatings technical field, it is related to a kind of TiZrB2Material, more particularly to A kind of TiZrB of (001) high preferred orientation2Hard coat and its preparation method and application.
Background technology
With the development and the progress of industrial technology of society, industrial circle proposes higher and higher want to the performance of material Ask, there is excellent combination property in many engineer applied application requirements materials；Do not require nothing more than it there is high hardness, it is corrosion-resistant Performance, also requires that it has low coefficient of friction, good high-temperature stability etc..To meet increasingly complicated and diversified engineering need Ask, coat one layer of hard coat in material surface, arisen at the historic moment with improving the protective coating of combination property of material.Hard is applied Layer can improve the surface property of material, reduce the friction and wear with workpiece, it is effective improve material surface hardness, it is toughness, resistance to Mill property and high-temperature stability, increase substantially the service life of coating product.Hard protection coatings are mainly made up of metallic bond Transition metal nitride, carbide, boride and the metal oxide that is made up of ionic bond etc. formed, these are with ceramic material Coating based on material has the characteristics such as high rigidity, high chemical stability, but the toughness of film layer is often poor, holds in use The brittle failure such as easily fall off, peel off, this makes the application of coating by a definite limitation.In fact, it is sufficiently high for hardness Hard coat, failure be more dependent on toughness, chemical stability and fatigue resistance of coating etc..Therefore, design and develop A kind of coating with certain degree of hardness and excellent toughness and decay resistance is to compel to be essential with the service life for quickly improving coating The technical barrier to be solved.
TiB2With high rigidity, high-melting-point, low-density, higher Young's modulus, good heat conduction, conduction, wear-resisting and change The advantages of learning stability, is a kind of advanced ceramics material with excellent 26S Proteasome Structure and Function performance, therefore it widely should For multiple fields, especially as coating materials such as hard, protection, electrical contacts.But TiB2The fragility of ceramic material It is limited to a certain extent to be used alone.
In recent years, due to multiphase composite coating protective coating using on shown relative to single coating it is more excellent Mechanics, chemistry and the sassafras that rubs the performance such as learn and received significant attention.The compound mode of multiphase has a variety of, such as ceramics/Ceramic Composite, pottery Porcelain/metal composite and sandwich construction etc..The research of wherein ceramic/metal composite coating is the most extensive, passes through the incorporation of metal Improve toughness, frictional behaviour of ceramics etc..Therefore, the Research Thinking of Material cladding is used for reference, based on TiB2The high rigidity of material, TiB2The enhanced metal-base composites of particle has been widely studied recently.However, the TiB in material2It is intended only as enhancing mutually few Amount is made an addition to inside metallic matrix, and this improvement to the strength of materials and hardness is extremely limited.Conversely, with TiB2For oikocryst The report for being added the material being combined with a small amount of metal phase is actually rare.And the metal Zr doping TiB prepared by magnetron sputtering2Apply Layer does not appear in the newspapers then.
The content of the invention
In order to solve shortcoming and defect part of the prior art, primary and foremost purpose of the invention is that providing one kind both had High rigidity has good toughness again, while friction resistant, polishing machine, electric conductivity and resistance to chemical corrosion show good TiZrB2Hard coat；
Another object of the present invention is to provide a kind of above-mentioned TiZrB2The preparation method of hard coat；This method is not only made Standby cost is low and simple to operate, short preparation period, repeatability are strong, available for large-scale industrial production.
It is still another object of the present invention to provide above-mentioned TiZrB2The application of hard coat.
The object of the invention is achieved through the following technical solutions：
A kind of TiZrB2Hard coat, the coating is with TiB2For principal crystalline phase, metal Zr is time crystalline phase, utilizes physical vapor The composite coating material that deposition technique is composited on matrix, wherein TiB2Content be 65~95at.%, Zr contents be 5~ 35at.%.
The physical gas phase deposition technology is that bipolar pulse magnetron sputtering technique, vacuum evaporation technology or Assisted by Ion Beam are heavy Product technology.
Described matrix is monocrystalline silicon, glass, high-speed steel, steel alloy or titanium alloy.
The thickness of the coating is 1.0~1.3 μm.
Above-mentioned TiZrB2The preparation method of hard coat, with TiB2Ceramic target and metal Zr targets are raw material, using impulse magnetron Sputtering technology, in-situ deposition difference TiB2The coating matched with Zr, is concretely comprised the following steps：
S1. matrix is cleaned：Matrix after polished processing is sent into supersonic wave cleaning machine, successively with acetone, absolute ethyl alcohol 10~20min of ultrasonic cleaning is carried out with 15~30kHz respectively, then cleaned with deionized water, then with the nitrogen of purity >=99.5% Air-blowing is done；
S2. vacuumize and clean plated film cavity with ion beam etching：Matrix after ultrasonic cleaning is placed in the workpiece of vacuum chamber On support, vacuum 5.0 × 10 is evacuated to-3Below Pa, later on ion gun is passed through 80~100sccm argon gas to ion gun, if The power for putting ion gun is 0.9kW, and the bias for setting work support is -300~-500V, etch cleaner process continues 20~ 30min；
S3. ion beam etching matrix：Matrix is placed in front of ion gun, it is -300~-500V, working time to set bias For 15~20min；
S4.TiZrB2The preparation of hard coat：Using the method for bipolar pulse magnetron sputtering, matrix and support ginseng are set The distance of number, target and matrix, is passed through 80~100sccm of argon gas, controls 0.5~0.6Pa of gas pressure in vacuum, opens and set electricity Source parameter, wherein TiB2Ceramic target is A targets, and metal zirconium target is B targets, by sample baffle plate transposition in TiB2Ceramic target and metal zirconium target Before, build-up of luminance after 10~15min of pre-sputtering, opens sample baffle plate, starts sputtering sedimentation TiZrB2Hard coat, sputtering time is 3h；
S5. deposition terminates, and closes power supply, treats that vacuum room temperature is down to room temperature, and air is filled toward vacuum chamber, opens vacuum chamber and takes Go out sample, in matrix surface formation TiZrB2Hard coat.
Matrix and support parameter are described in step S4：Substrate bias -100~-300V, support rotation 3rpm/min is public Turn 2~5rpm/min, 300 DEG C of depositing temperature is set.
Power parameter is described in step S4：Frequency 40kHz, 3~4kW of power, the dutycycle of the A target pulse powers for 25~ 75%.
The distance of target and matrix described in step S4 is 6~10cm.
Above-mentioned TiZrB2Application of the hard coat in the surfacecti proteon field of cutter, mould and microelectronics.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) coating hardness is up to more than 28GPa, and electric conductivity is good, while having good toughness and anticorrosive, anti- Ablation property and excellent friction, polishing machine.
(2) TiZrB is prepared2Coating it is easy to operate, technique is simple, and short preparation period, cost is low, is easy to large-scale industry Metaplasia is produced.
Brief description of the drawings
Fig. 1 is TiZrB prepared by the present invention2Surface (XRD) collection of illustrative plates of coating sample, wherein abscissa are the θ of the angle of diffraction 2, Unit for °, ordinate is diffraction peak intensity, and unit is a.u..
Fig. 2 is TiZrB prepared by the present invention2ESEM (SEM) photo of coating sample, wherein a is surface, and b is disconnected Face.
Fig. 3 is TiZrB prepared by the present invention2The cut microstructure figure of coating sample.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
1st, prepare：
S1. the TiB of commercially available purity 99.9% is selected2The metal Zr targets of ceramic target and commercially available purity 99.99% are raw material；Matrix Material selection WC-Co hard alloy.
S2. matrix is cleaned：WC-Co hard alloy matrix after polished processing is sent into supersonic wave cleaning machine, used successively Acetone, absolute ethyl alcohol carry out ultrasonic cleaning 10min respectively with 30kHz, are then cleaned with deionized water, then with purity >=99.5% Nitrogen drying.
S3. vacuumize and ion beam etching cleaning chamber and matrix：Ion plating equipment installs TiB2Flat target and metal Zr Style Columu Talget, coating chamber is cleaned with high power dust catcher；Matrix after ultrasonic cleaning is placed on the work support of vacuum chamber, is evacuated to Vacuum 5.0 × 10-3Below Pa, later on ion gun is passed through 80sccm argon gas to ion gun, sets ion source power 0.9kW, sets work support bias -300V, and this etching cleaning process continues 20min.
S4. ion beam etching matrix：Pivoted frame is rotated, by matrix as in front of ion gun, bias -500V is set, during work Between be 20min.
S5. argon gas 80sccm is passed through, gas pressure in vacuum 0.56Pa is controlled, using the method for bipolar pulse magnetron sputtering, TiB2Ceramic target is A targets, and metal Zr targets are B targets, and the distance of target and matrix is 10cm, sets matrix and the support parameter to be：Base Body-bias -100V, support rotation 3rpm/min, revolve round the sun 2rpm/min, sets 300 DEG C of depositing temperature；Open and set power supply to join Number is：Frequency 40kHz, the dutycycle of power 4kW, A target pulse power are 75%；By sample baffle plate transposition in two sputtering targets Before, build-up of luminance is carried out after pre-sputtering 10min, opens sample baffle plate, starts formal sputtering depositing Ti ZrB2Hard coat, during deposition Between be 3h.
S6. deposition terminates, and closes power supply, treats that vacuum room temperature is down to room temperature, and air is filled toward vacuum chamber, opens vacuum chamber and takes Go out sample, in WC-Co hard alloy matrix surface formation TiZrB2Hard coat.
2nd, performance test：
By the TiZrB of preparation2Hard coat typical sample carries out analysis test, obtains following result and data.By gained TiZrB2The pungent Alpha-Step IQ types surface profiler for weeding scientific and technological Engineering Co., Ltd's production in the hard coat sample U.S. is surveyed It is 1.2 μm or so to try coating layer thickness.By the TiZrB of gained2Hard coat sample is using German Brooker company production D8Advance types X-ray diffractometer analysis sample surfaces crystalline phase composition, it is seen that prepared TiZrB2TiB in coating2Diffraction Peak is stronger, and Zr diffraction maximum is not obvious (Fig. 1).The S-4800 type Scanning Electron microscopes pair produced using HIT Prepared TiZrB2Coating sample carries out surface and section microstructure analysis, can from the microphoto (Fig. 2) of coating surface To find out that the coating surface is more smooth, fine and close and is produced without micro-crack；Can substantially it be sent out from the cross-section photomicrograph of coating Now the uniform coating thickness, crystal are in the form of a column growth, arrangement closely.With Anton Paar NHT2 type nano-hardness tester testing coating hardness And modulus of elasticity, as a result show, TiZrB2Coating shows good toughness, and elastic resilience is up to 50%；Measure coating hard Degree reaches 32Gpa；It is 0.23 that coefficient of friction is measured with HSR-2M coating friction wear testing machines, after sample abrasion 1h, has no mistake Effect, it is seen that TiZrB2Coating has good wear Characteristics.Coating residual compressive stress is measured with fast general membrane stress instrument 0.7Gpa；With Anton Paar MST types nano impress instrument test result as shown in figure 3, there it can be seen that cut increases with load Plus, cut gradually broadens, load increase depth increase, does not go out without film layer obscission, and in scoring groove around cut , there is more smooth groove, as a result shows the TiZrB in the case where Hardness loss is little in existing crackle2Coating is shown preferably Toughness.Coated film base junction closes critical load and reaches 10GPa, and coating adhesion property is excellent；Finally by obtained TiZrB2Coating exists Acid-fast alkali-proof corrosion test is carried out under normal temperature, is as a result shown, TiZrB2Coating has good chemical stability.
Embodiment 2
S1. the TiB of commercially available purity 99.9% is selected2The metal Zr targets of ceramic target and commercially available purity 99.99% are raw material, matrix The monocrystalline silicon being orientated from (100).
S2. matrix is cleaned：The single crystal silicon substrate of (100) orientation after polished processing is sent into supersonic wave cleaning machine, according to It is secondary that ultrasonic cleaning 10min is carried out with 30kHz respectively with acetone, absolute ethyl alcohol, then rinsed with deionized water, then with purity >= 99.5% nitrogen drying.
S3. vacuumize and ion beam etching cleaning chamber and matrix：Ion plating equipment installs TiB2Flat target and metal Zr Style Columu Talget, coating chamber is cleaned with high power dust catcher.Matrix after ultrasonic cleaning is placed on the work support of vacuum chamber, vacuum Room is vacuumized, to vacuum 5.0 × 10-3Below Pa, later on ion gun is passed through 80sccm argon gas to ion gun, sets ion Source power 0.9kW, sets work support to bias 300V, and this etching cleaning process continues 20min.
S4. ion beam etching matrix：Pivoted frame is rotated, by matrix as in front of ion gun, bias -500V is set, during work Between be 20min.
S5. argon gas 80sccm is passed through, gas pressure in vacuum 0.56Pa is controlled, using the method for bipolar pulse magnetron sputtering, TiB2Ceramic target is A targets, and metal Zr targets are B targets, and the distance of target and matrix is 6cm, sets matrix and the support parameter to be：Matrix Bias -300V, support rotation 3rpm/min, revolve round the sun 5rpm/min, sets 300 DEG C of depositing temperature.Open and power parameter is set For：Frequency 40kHz, the dutycycle of power 4kW, A target pulse power are 25%.By sample baffle plate transposition in two sputtering targets Before, build-up of luminance is carried out after pre-sputtering 15min, removes sample baffle plate, starts formal sputtering depositing Ti ZrB2Hard coat, during deposition Between 3h.
S5. deposition terminates, and closes power supply, treats that vacuum room temperature is down to room temperature, toward vacuum chamber inflation, opens vacuum chamber and takes out Sample, the single crystal silicon substrate surface being orientated in (100) forms required TiZrB2Coating.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (9)

1. a kind of TiZrB2Hard coat, it is characterised in that：The coating is with TiB2For principal crystalline phase, metal Zr is time crystalline phase, is utilized The composite coating material that physical gas phase deposition technology is composited on matrix, wherein TiB2Content is 65~95at.%, and Zr contains Measure as 5~35at.%.
2. a kind of TiZrB according to claim 12Hard coat, it is characterised in that：The physical gas phase deposition technology is Bipolar pulse magnetron sputtering technique, vacuum evaporation technology or ion beam assisted deposition.
3. a kind of TiZrB according to claim 12Hard coat, it is characterised in that：Described matrix be monocrystalline silicon, glass, High-speed steel, steel alloy or titanium alloy.
4. a kind of TiZrB according to claim 12Hard coat, it is characterised in that：The thickness of the coating be 1.0~ 1.3μm。
5. a kind of TiZrB according to claim 12The preparation method of hard coat, it is characterised in that：With TiB2Ceramic target It is raw material with metal Zr targets, using pulsed magnetron sputtering technology, in-situ deposition difference TiB2The coating matched with Zr, specific steps For：
S1. matrix is cleaned：Matrix after polished processing is sent into supersonic wave cleaning machine, successively with acetone, absolute ethyl alcohol with 15 ~30kHz carries out 10~20min of ultrasonic cleaning respectively, is then cleaned with deionized water, then is blown with the nitrogen of purity >=99.5% It is dry；
S2. vacuumize and clean plated film cavity with ion beam etching：Matrix after ultrasonic cleaning is placed in the work support of vacuum chamber On, it is evacuated to vacuum 5.0 × 10-3Below Pa, later on ion gun is passed through 80~100sccm argon gas to ion gun, set from The power of component is 0.9kW, and the bias for setting work support is -300~-500V, and etch cleaner process continues 20~30min；
S3. ion beam etching matrix：Matrix is placed in front of ion gun, it is -300~-500V to set bias, and the working time is 15 ~20min；
S4.TiZrB2The preparation of hard coat：Using the method for bipolar pulse magnetron sputtering, matrix and support parameter, target are set With the distance of matrix, 80~100sccm of argon gas is passed through, 0.5~0.6Pa of gas pressure in vacuum is controlled, opens and power parameter is set, Wherein TiB2Ceramic target is A targets, and metal zirconium target is B targets, by sample baffle plate transposition in TiB2Before ceramic target and metal zirconium target, build-up of luminance, After 10~15min of pre-sputtering, sample baffle plate is opened, starts sputtering sedimentation TiZrB2Hard coat, sputtering time is 3h；
S5. deposition terminates, and closes power supply, treats that vacuum room temperature is down to room temperature, and air is filled toward vacuum chamber, opens vacuum chamber and takes out sample Product, in matrix surface formation TiZrB2Hard coat.
6. preparation method according to claim 5, it is characterised in that：Matrix and support parameter are described in step S4：Base Body-bias -100~-300V, support rotation 3rpm/min, revolve round the sun 2~5rpm/min, sets 300 DEG C of depositing temperature.
7. preparation method according to claim 5, it is characterised in that：Power parameter is described in step S4：Frequency 40kHz, 3~4kW of power, the dutycycle of the A target pulse powers are 25~75%.
8. preparation method according to claim 5, it is characterised in that：The distance of target and matrix described in step S4 is 6 ~10cm.
9. TiZrB according to claim 12Hard coat answering in the surfacecti proteon field of cutter, mould and microelectronics With.
CN201710141355.6A 2017-03-10 2017-03-10 TiZrB2Hard coating and preparation method and application thereof Active CN107012424B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107740043A (en) * 2017-10-25 2018-02-27 深圳先进技术研究院 Adulterate CaF2TiB2Coating, CaF2And TiB2Composite coating, its preparation method and application and cutter
CN112323031A (en) * 2020-10-16 2021-02-05 吉林大学 High-hardness corrosion-resistant coating and preparation method and application thereof
CN112609157A (en) * 2020-11-20 2021-04-06 江苏科技大学 Wide-temperature-range self-lubricating nano multilayer film material and preparation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1032510A (en) * 1987-10-09 1989-04-26 康宁玻璃公司 Insert chip for ceramic cutting-tool
CN103160776A (en) * 2011-12-15 2013-06-19 中国科学院宁波材料技术与工程研究所 Titanium diboride-nickel coating or film and preparation method thereof
CN103160777A (en) * 2011-12-15 2013-06-19 中国科学院宁波材料技术与工程研究所 Titanium diboride-nickel thin film with coating structure and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1032510A (en) * 1987-10-09 1989-04-26 康宁玻璃公司 Insert chip for ceramic cutting-tool
CN103160776A (en) * 2011-12-15 2013-06-19 中国科学院宁波材料技术与工程研究所 Titanium diboride-nickel coating or film and preparation method thereof
CN103160777A (en) * 2011-12-15 2013-06-19 中国科学院宁波材料技术与工程研究所 Titanium diboride-nickel thin film with coating structure and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107740043A (en) * 2017-10-25 2018-02-27 深圳先进技术研究院 Adulterate CaF2TiB2Coating, CaF2And TiB2Composite coating, its preparation method and application and cutter
CN112323031A (en) * 2020-10-16 2021-02-05 吉林大学 High-hardness corrosion-resistant coating and preparation method and application thereof
CN112609157A (en) * 2020-11-20 2021-04-06 江苏科技大学 Wide-temperature-range self-lubricating nano multilayer film material and preparation

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