CN103160776B - Titanium diboride-nickel coating or film and preparation method thereof - Google Patents

Titanium diboride-nickel coating or film and preparation method thereof Download PDF

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CN103160776B
CN103160776B CN201110418928.8A CN201110418928A CN103160776B CN 103160776 B CN103160776 B CN 103160776B CN 201110418928 A CN201110418928 A CN 201110418928A CN 103160776 B CN103160776 B CN 103160776B
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tib
coating
substrate
film
target
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CN103160776A (en
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黄峰
葛芳芳
王博
王怀勇
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention relates to a preparation method of a titanium diboride-nickel coating or film. By using the method, a metal Ni toughened TiB2 coating or film is prepared through in-situ synthesis; and the coating has hardness up to higher than 25GPa, good conductive properties, good toughness, corrosion resistance and erosion resistance, and excellent friction and wear performance, and can be widely applied to the fields of cutting tool, mold, electric contact and protection. The preparation process has advantages of simpleness, short production cycle and low cost, and is convenient for industrialized mass production.

Description

The preparation method of a kind of TiB2-nickel coating or film
Technical field
The invention belongs to field of new, relate to a kind of TiB 2-Ni material, is specifically related to the TiB that a kind of W metal of fabricated in situ is toughness reinforcing 2the preparation method of coating or film.
Background technology
TiB 2there is the advantages such as high rigidity, high-melting-point, low density, higher Young's modulus, good heat conduction, conduction, wear-resisting and chemical stability, it is a kind of advanced ceramics material with excellent structure and function performance, therefore it is widely used in multiple fields, particularly can as coated materials such as hard, protection, electrical contacts.But TiB 2the fragility of stupalith limits it to a certain extent and applies separately, therefore, uses for reference the Research Thinking of Material cladding, based on TiB 2the high rigidity of material, TiB 2the metal-base composites of particle reinforce is widely studied recently.Such as: titanium diboride dispersed and strengthened copper-based composite material (Chinese patent, 200910095176.9), TiB 2particle reinforced magnesium base compound material (Chinese patent, 200710047943.X) etc., these materials well maintain the premium properties such as toughness, electroconductibility, workability of metallic matrix, improve again intensity and the hardness of metal to a certain extent, have good application prospect.But, the TiB in material 2just as wild phase a small amount of make an addition to metallic matrix inside, this is extremely limited to the improvement of the strength of materials and hardness.Otherwise, with TiB 2for the report of the principal crystalline phase in addition material of a small amount of metallographic phase compound is actually rare.The TiB that Zhang Xinghong etc. will obtain in advance 2phase and metallographic phase obtain TiB by techniques such as sintering 2content Gao get Da 75% and the lower block composite material of Cu-Ni content, obtained material is close to equilibrium state.(Xinghong Zhang, Changqing Hong, Jiecai Hana and Hexin Zhang, Microstructure and mechanical properties ofTiB 2/ (Cu, Ni) interpenetrating phase composites, Scripta Materialia, 55,2006,565 – 568) and the toughness reinforcing TiB of the W metal of original position vapor-phase synthesis 2coating or film do not appear in the newspapers.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of TiB 2the preparation method of-Ni coating or film, not only preparation cost is low, and simple to operate, preparation cycle is short, repeatability is strong, can be used for large-scale commercial production.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of TiB 2the preparation method of-Ni coating or film, is characterized in that with highly purified TiB 2ceramic target and W metal target are raw material, adopt physical gas phase deposition technology, by in-situ deposition different Ti B 2with coating or the film of Ni proportioning, as preferably, the concrete steps that magnetron sputtering technique prepares this coating or film are:
A) target and substrate are installed;
B) to vacuumize and base plate heating;
C) pass into rare gas element, power supply and substrate parameter are set, build-up of luminance, after pre-sputtering, sputtering sedimentation;
D) deposition terminates, and closes electricity, gas, water route, sampling.
As improvement, described step substrate a) will use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning 10 ~ 20min in a pre-installation successively respectively, then forced air drying 1 ~ 2h at 70 ~ 90 DEG C.
As preferably, described step b) in vacuumize and refer to that in sediment chamber, back end vacuum is lower than 9.5 × 10 -4pa, described base plate heating temperature is room temperature ~ 500 DEG C, insulation 20 ~ 30min.
Described step c) in power supply and substrate parameter be: TiB 2ceramic target power parameter is: intermediate frequency 50-200KHZ, power 100-500W, dutycycle 60-90%; Ni metallic target power parameter is: dc power 0-20W; The pre-sputtering time is 8 ~ 15min, and the described sputtering sedimentation time is 30 ~ 200min.Substrate parameter is: bias voltage 0V, temperature room temperature ~ 500 DEG C.
Preferred again, described step c) in the rare gas element passed into be argon gas, inert gas flow controls at 20-40sccm, and by the scope of sediment chamber's internal gas pressure modulation 0.1-1Pa.
TiB prepared by aforesaid method 2-Ni coating or film are with TiB 2for principal crystalline phase, W metal is that paracrystalline phase utilizes physical gas phase deposition technology In-situ reaction, wherein TiB 2content is 65-95at.%, Ni content is 5-35at.%.
TiB 2the baseplate material of-Ni coating or film selects silicon single crystal, glass, rapid steel, steel alloy or titanium alloy etc.
The thickness of film is 20nm-1um; The thickness of coating is 1um-1mm.
Compared with prior art, the invention has the advantages that:
1) a kind of new coating material system is devised, the TiB that namely W metal of fabricated in situ is toughness reinforcing 2coating or film.
2) this coating hardness is up to more than 25GPa, and conductivity is good, has the friction of good toughness and anticorrosive, anti-yaw damper performance and excellence, polishing machine simultaneously.
3) TiB is prepared 2the technique of-Ni coating or film is simple, and easy to operate, preparation cycle is short, and cost is low, is convenient to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares TiB 2-Ni coating sample surface (XRD) collection of illustrative plates, wherein X-coordinate is diffraction angle 2 θ, and unit is °, and ordinate zou is diffraction peak intensity, and unit is a.u.;
Fig. 2 the present invention prepares TiB 2scanning electron microscope (SEM) photo of-Ni coating sample, wherein a is section, and b is surface.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1:
1) TiB of commercially available purity 99.9% is selected 2the W metal target of ceramic target and commercially available purity 99.99% is raw material; The monocrystalline silicon substrate of orientation that substrate is selected (100).
2) first carry out the cleaning of substrate, use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning substrate 20min successively respectively, then forced air drying 2h at 80 DEG C, for subsequent use.
3) magnetic control sputtering system that this seminar autonomous design is produced is adopted, first begin to speak after correct installation base plate and target, first check that gas, electricity, water route are all normal, then open general supply, start mechanical pump, when sediment chamber and sample chamber air pressure be all in 10Pa once after, closedown mechanical pump and chamber between valve, open flapper valve, start molecular pump, slide valve of outwarding winding, when sample house vacuum reaches 10 -3after Pa, stop carefully taking out its vacuum, to accelerate the extraction speed depositing house vacuum.
4) when back end vacuum in sediment chamber reaches 8.7 × 10 -5during Pa, open sample substrate heating mode, set temperature is 200 DEG C, is incubated 20min, treats that vacuum tightness is evacuated to 9.1 × 10 after arriving assigned temperature -5back end vacuum tightness is recorded during Pa.
5) open argon bottle, flow control is at 30sccm, and corresponding valve of outwarding winding, passes into rare gas element, suitably closes the slide valve between sediment chamber and molecular pump, by sediment chamber's internal gas pressure modulation 0.5Pa.
6) TiB is set 2ceramic target power parameter is: intermediate frequency (MF) 100HKZ, power 400W, dutycycle 80%; Ni metallic target power parameter is: direct current (DC), power 4W; After about pre-sputtering 10min, open sample baffle plate, formal sputtering deposits, depositing time: 180min.
7), after deposition terminates, sample baffle plate, target power supply, gas circuit etc. are closed successively; After sample cooling, sampling, namely can obtain final product TiB 2-Ni coating sample.
By the TiB of preparation 2-Ni coating typical sample carries out analytical test, obtains following result and data.By the TiB of gained 2-Ni coating sample is about 1.3 μm with the pungent Alpha-Step IQ type surface profiler testing coating thickness weeding scientific and technological Engineering Co., Ltd product of the U.S..By the TiB of gained 2the D8Advance type X – x ray diffractometer x analytic sample surface crystalline phase composition that-Ni coating sample adopts German Brooker company to produce, visible prepared TiB 2tiB in-Ni coating 2diffraction peak comparatively strong (150a.u.), and the diffraction peak of Ni not obvious (Fig. 1).Adopt the S-4800 type Scanning Electron microscope of HIT's production to prepared TiB 2-Ni coating sample carries out surface and section microstructure analysis, can find out that this coatingsurface is more smooth, fine and close and do not have tiny crack to produce from the Photomicrograph (Fig. 2) of coatingsurface; Obviously can find that this coat-thickness is homogeneous, crystal is columnar growth, arrangement tight from the cross-section photomicrograph of coating.To the TiB of gained 2the AXIS UTLTRADLD type XPS that-Ni coating sample adopts Japanese Shimadzu Corporation to produce analyzes, and shows that coat inside Ni content is probably 20.50%.By obtained TiB 2the frictional coefficient that-Ni coating sample records coating under the upper 5N power of multifunction friction wear trier (UMT-3) is about 0.68, and sample has no inefficacy after wearing and tearing 1 hour, visible TiB 2-Ni coating has good wear Characteristics.Finally by obtained TiB 2-Ni coating sample carries out acid-fast alkali-proof corrosion at normal temperatures, and result shows that coating stability is good.
Embodiment 2:
1) TiB of commercially available purity 99.9% is selected 2the W metal target of ceramic target and commercially available purity 99.99% is raw material; Ordinary plate glass substrate selected by substrate.
2) first carry out the cleaning of substrate, use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning substrate 20min successively respectively, then forced air drying 2h at 80 DEG C, for subsequent use.
3) magnetic control sputtering system that this seminar autonomous design is produced is adopted, first begin to speak after correct installation base plate and target, first check that gas, electricity, water route are all normal, then open general supply, start mechanical pump, when sediment chamber and sample chamber air pressure be all in 10Pa once after, closedown mechanical pump and chamber between valve, open flapper valve, start molecular pump, slide valve of outwarding winding, when sample house vacuum reaches 10 -3after Pa, stop carefully taking out its vacuum, to accelerate the extraction speed depositing house vacuum.
4) when back end vacuum in sediment chamber reaches 7 × 10 -5during Pa, open sample substrate heating mode, set temperature is 300 DEG C, is incubated 20min, treats that vacuum tightness is evacuated to 7.8 × 10 after arriving assigned temperature -5back end vacuum tightness is recorded during Pa.
5) open argon bottle, flow control is at 26sccm, and corresponding valve of outwarding winding, passes into rare gas element, suitably closes the slide valve between sediment chamber and molecular pump, by sediment chamber's internal gas pressure modulation 0.3Pa.
6) TiB is set 2ceramic target power parameter is: intermediate frequency (MF) 150HKZ, power 300W, dutycycle 90%; Ni metallic target power parameter is: direct current (DC), power 8W; After about pre-sputtering 10min, open sample baffle plate, formal sputtering deposits, depositing time: 30min.
7), after deposition terminates, sample baffle plate, target power supply, gas circuit etc. are closed successively; After sample cooling, sampling, namely can obtain final product TiB 2-Ni film sample.
Embodiment 3:
1) TiB of commercially available purity 99.9% is selected 2the W metal target of ceramic target and commercially available purity 99.99% is raw material; Rapid steel substrate selected by substrate.
2) first carry out the cleaning of substrate, use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning substrate 20min successively respectively, then forced air drying 2h at 80 DEG C, for subsequent use.
3) magnetic control sputtering system that this seminar autonomous design is produced is adopted, first begin to speak after correct installation base plate and target, first check that gas, electricity, water route are all normal, then open general supply, start mechanical pump, when sediment chamber and sample chamber air pressure be all in 10Pa once after, closedown mechanical pump and chamber between valve, open flapper valve, start molecular pump, slide valve of outwarding winding, when sample house vacuum reaches 10 -3after Pa, stop carefully taking out its vacuum, to accelerate the extraction speed depositing house vacuum.
4) when back end vacuum in sediment chamber reaches 5 × 10 -5during Pa, open sample substrate heating mode, set temperature is 500 DEG C, is incubated 30min, treats that vacuum tightness is evacuated to 5.8 × 10 after arriving assigned temperature -5back end vacuum tightness is recorded during Pa.
5) open argon bottle, flow control is at 20sccm, and corresponding valve of outwarding winding, passes into rare gas element, suitably closes the slide valve between sediment chamber and molecular pump, by sediment chamber's internal gas pressure modulation 0.2Pa.
6) TiB is set 2ceramic target power parameter is: intermediate frequency (MF) 50HKZ, power 400W, dutycycle 70%; Ni metallic target power parameter is: direct current (DC), power 18W; After about pre-sputtering 10min, open sample baffle plate, formal sputtering deposits, depositing time: 40min.
7), after deposition terminates, sample baffle plate, target power supply, gas circuit etc. are closed successively; After sample cooling, sampling, namely can obtain final product TiB 2-Ni coating sample.
Embodiment 4:
1) TiB of commercially available purity 99.9% is selected 2the W metal target of ceramic target and commercially available purity 99.99% is raw material; Titanium alloy substrate selected by substrate.
2) first carry out the cleaning of substrate, use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning substrate 15min successively respectively, then forced air drying 1h at 80 DEG C, for subsequent use.
3) magnetic control sputtering system that this seminar autonomous design is produced is adopted, first begin to speak after correct mounting plate and target, first check that gas, electricity, water route are all normal, then open general supply, start mechanical pump, when sediment chamber and sample chamber air pressure be all in 10Pa once after, closedown mechanical pump and chamber between valve, open flapper valve, start molecular pump, slide valve of outwarding winding, when sample house vacuum reaches 10 -3after Pa, stop carefully taking out its vacuum, to accelerate the extraction speed depositing house vacuum.
4) when back end vacuum in sediment chamber reaches 8 × 10 -5during Pa, record back end vacuum tightness.
5) open argon bottle, flow control is at 35sccm, and corresponding valve of outwarding winding, passes into rare gas element, suitably closes the slide valve between sediment chamber and molecular pump, by sediment chamber's internal gas pressure modulation 0.8Pa.
6) TiB is set 2ceramic target power parameter is: intermediate frequency (MF) 100HKZ, power 200W, dutycycle 80%; Ni metallic target power parameter is: direct current (DC), power 15W; After about pre-sputtering 10min, open sample baffle plate, formal sputtering deposits, depositing time: 180min.
7), after deposition terminates, sample baffle plate, target power supply, gas circuit etc. are closed successively; After sample cooling, sampling, namely can obtain final product TiB 2-Ni coating sample.

Claims (2)

1. a preparation method for TiB2-nickel coating or film, is characterized in that with TiB 2ceramic target and W metal target are raw material, adopt physical gas phase deposition technology, in-situ deposition different Ti B 2with coating or the film of Ni proportioning, concrete steps are:
A) target and substrate are installed;
B) to vacuumize and base plate heating; Vacuumize and refer to that in sediment chamber, back end vacuum is lower than 9.5 × 10 -4pa, described base plate heating temperature is room temperature ~ 500 DEG C, insulation 20 ~ 30min;
C) pass into rare gas element, power supply and substrate parameter are set, build-up of luminance, after pre-sputtering, sputtering sedimentation; The rare gas element passed into is argon gas, and inert gas flow controls at 20-40sccm, and by the scope of sediment chamber's internal gas pressure modulation 0.1-1Pa; Power supply and substrate parameter are: TiB 2ceramic target power parameter is: intermediate frequency 50-200KHZ, power 100-500W, dutycycle 60-90%; Ni metallic target power parameter is: dc power 0-20W; The pre-sputtering time is 8 ~ 15min, and the described sputtering sedimentation time is 30 ~ 200min; Substrate parameter is bias voltage 0V, temperature room temperature ~ 500 DEG C;
D) deposition terminates, and closes electricity, gas, water route, sampling.
2. preparation method according to claim 1, is characterized in that described step substrate a) will use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning 10 ~ 20min in a pre-installation successively respectively, then forced air drying 1 ~ 2h at 70 ~ 90 DEG C.
CN201110418928.8A 2011-12-15 2011-12-15 Titanium diboride-nickel coating or film and preparation method thereof Active CN103160776B (en)

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CN103451648B (en) * 2013-09-02 2016-05-04 山东大学 A kind of laser melting coating TiB2-Ni based metal ceramic coating and preparation method thereof
CN103849834A (en) * 2014-02-20 2014-06-11 西工大常熟研究院有限公司 Compound cutting tool coating based on titanium diboride and preparation method thereof
KR20160001514A (en) * 2014-06-27 2016-01-06 삼성전자주식회사 Electrically conductive thin films
CN107012424B (en) * 2017-03-10 2020-09-08 广东工业大学 TiZrB2Hard coating and preparation method and application thereof
CN107338418A (en) * 2017-08-30 2017-11-10 深圳先进技术研究院 Transition metal boride metal composite target, filming equipment and application thereof
CN110729445A (en) * 2018-07-16 2020-01-24 深圳先进技术研究院 Tab with coating, preparation method thereof, battery cell, battery and electric tool
CN115612984B (en) * 2022-09-09 2024-09-20 中国科学院金属研究所 Titanium diboride coating with stress and structural gradient and preparation method thereof

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Publication number Priority date Publication date Assignee Title
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JPS59134608A (en) * 1983-01-20 1984-08-02 Tatsuro Kuratomi Drill of hard sintered alloy and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394170A (en) * 1979-11-30 1983-07-19 Nippon Oil And Fats Company, Limited Composite sintered compact containing high density boron nitride and a method of producing the same
JPS59134608A (en) * 1983-01-20 1984-08-02 Tatsuro Kuratomi Drill of hard sintered alloy and manufacturing method thereof

Non-Patent Citations (1)

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Title
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