CN103160777B - Titanium diboride-nickel thin film with coating structure and preparation method thereof - Google Patents
Titanium diboride-nickel thin film with coating structure and preparation method thereof Download PDFInfo
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- CN103160777B CN103160777B CN201110418976.7A CN201110418976A CN103160777B CN 103160777 B CN103160777 B CN 103160777B CN 201110418976 A CN201110418976 A CN 201110418976A CN 103160777 B CN103160777 B CN 103160777B
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Abstract
The invention relates to a titanium diboride-nickel thin film with coating structure. The TiB2-Ni thin film is characterized by being prepared from a continuous phase metal Ni and a dispersed phase TiB2 grains through in-situ synthesis. In the TiB2-Ni thin film, metal Ni in a three-dimensional continuous cellular structure uniformly form a basic framework of the thin film, and the TiB2 grains in granular shape uniformly fill in the cellular structure, so as to form a coating microstructure with metal Ni evenly coated with TiB2 grains; and the TiB2 accounts for 60- 95at.%, and Ni accounts for 5-40at.%. The TiB2-Ni thin film with coating structure provided by the invention shows good toughness and high hardness, so as to greatly expand the scope of application of the thin film. A double-target co-sputtering magnetron sputtering technology is easy to operate; composition, structure and performance of the TiB2-Ni thin film material can be well controlled through control of process conditions; and the method does not require a post-treatment process, has short preparation period, low cost and good reproducibility, and is easy to realize industrialized production.
Description
Technical field
The invention belongs to field of new, relate to a kind of TiB
2-Ni film, specifically a kind of TiB of clad structure
2-Ni film and preparation method thereof.
Background technology
TiB
2having the advantages such as high rigidity, high-melting-point, low density, higher Young's modulus, good heat conduction, conduction, wear-resisting and chemical stability, is a kind ofly have excellent structure properties and the advanced ceramics material of functional performance.Based on TiB
2the high rigidity of material, TiB
2the metal-base composites of particle reinforce is widely studied.Such as: titanium diboride dispersed and strengthened copper-based composite material (Chinese invention patent, 200910095176.9), TiB
2particle reinforced magnesium base compound material (Chinese invention 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, there is good application prospect.But, the TiB in material
2just as a small amount of (the usual TiB of wild phase
2≤ 20at.%) be distributed in metallic matrix inside, this is extremely limited to the improvement of the strength of materials and hardness.
In order to improve hardness and the intensity of metallic substance further, the present invention proposes a kind of new mentality of designing, substantially increases wild phase TiB in material
2content and a kind of rich TiB
2the thin-film material of phase, simultaneously in order to better keep the toughness of original W metal, the present invention constructs a kind of clad structure, both a kind of Ni nanoparticle layer three-dimensional wrapping TiB
2born of the same parents' shape microstructure of particle, has the TiB of this clad structure
2there is not been reported for-Ni film.
Up to the present, the preparation method of film has a variety of, is mainly divided into chemical process and the large class of physical method two.Wherein physical gas phase deposition technology enters gas phase through physical process due to source material, and under low pressure carries out, and therefore film is combined with matrix well, be convenient to large-scale continuous industrial production, thus development in recent years is rapid simultaneously.The present invention adopts industrial applications magnetron sputtering technique preparation the most widely in physical gas phase deposition technology to have the TiB of clad structure
2-Ni film.
Summary of the invention
First technical problem to be solved by this invention builds a kind of TiB with clad structure
2-Ni film, the film of this structure had both had good toughness, had again good hardness and intensity.
Second technical problem to be solved by this invention is to provide a kind of TiB with clad structure
2the preparation method of-Ni film, preparation technology is simple, and the cycle is short, and cost is low, and reproducibility is good, is convenient to realize suitability for industrialized production.
The present invention solves the technical scheme that above-mentioned first technical problem adopt: a kind of TiB with clad structure
2-Ni film, is characterized in that this TiB
2-Ni film take W metal as external phase, TiB
2crystal grain is that disperse phase In-situ reaction forms, at this TiB
2in-Ni film, W metal is evenly formed the basic boom of film with the continuous cell structure of three-dimensional, and TiB
2crystal grain then fills up inner at cell structure uniformly with particulate state, forms W metal and evenly wraps up TiB
2the coated microstructure of crystal grain, wherein TiB
2content is 60-95at.%, Ni content is 5-40at.%.
As preferably, described TiB
2the baseplate material of-Ni film selects silicon single crystal, glass, rapid steel, steel alloy, titanium alloy, copper alloy or nickelalloy etc.
Described TiB
2tiB in-Ni film
2cellular crystal grain is of a size of 2-80nm, and the thickness of its outer evenly W metal layer of parcel is 0.5-20nm.
The present invention solves the technical scheme that above-mentioned second technical problem adopt: a kind of TiB with clad structure
2the preparation method of-Ni film, is characterized in that with high-purity TiB
2ceramic target and W metal target are raw material, and adopt magnetic control sputtering system to utilize two target codeposition technique to be prepared, step is:
A) target, substrate are installed;
B) to vacuumize and base plate heating: back end vacuum is lower than 5 × 10
-5pa, the heating temperature range of substrate is room temperature-500 DEG C, and is incubated 20-30min.
C) pass into rare gas element, power supply and substrate parameter are set, build-up of luminance, after pre-sputtering, sputtering sedimentation, wherein TiB
2ceramic target power parameter is: intermediate frequency (MF) 50-200KHZ, power 100-500W, dutycycle 60-90%; Ni metallic target power parameter is: direct current (DC), power 0-20W; Substrate parameter is: bias voltage-100-0V, temperature room temperature-500 DEG C; Pre-sputtering time 8 ~ 15min; Depositing time: 10-120min;
D) deposition terminates, and closes electricity, gas, water route, sampling.
As improvement, described step substrate a) needs to use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning 10 ~ 20min successively before installing, then forced air drying 1 ~ 2h at 70 ~ 90 DEG C.
Finally, described step c) in the rare gas element that passes into be preferably argon gas, inert gas flow controls at 20-40sccm, and by the scope of sediment chamber's internal gas pressure modulation 0.1-1Pa.
Compared with prior art, the invention has the advantages that:
1) TiB has been constructed
2a kind of new microstructure of-Ni film, the i.e. TiB that wraps up fully continuously of the W metal of fabricated in situ
2film.
2) TiB of clad structure of the present invention
2-Ni film, is different from traditional TiB
2particulate reinforcement metal-base composites, show good toughness and very high hardness, this greatly expands the range of application of this film.
3) fabricated in situ clad structure TiB of the present invention
2the technology of preparing of-Ni film, easy to operate, without the need to aftertreatment technology, preparation cycle is short, and cost is low, and reproducibility is good, is convenient to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 the present invention prepares TiB
2-Ni film typical 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
2transmission electron microscope (TEM) photo of-Ni film typical sample;
Fig. 3 the present invention prepares TiB
2scanning electron microscope (SEM) photo of cut after-Ni film typical sample friction testing.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1:
1) select commercially available purity be 99.9% TiB
2ceramic target and commercially available purity be 99.99% W metal target be raw material; The monocrystalline silicon substrate of orientation that substrate is selected (100).
2) first carry out the cleaning of matrix, use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning substrate 15min successively respectively, then forced air drying 2h at 80 DEG C, for subsequent use.
3) two target magnetic control sputtering systems that this seminar autonomous design is produced are adopted, first after beginning to speak that matrix and target are correctly installed, 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 3.7 × 10
-5during Pa, open sample substrate heating mode, set temperature is 300 DEG C, is incubated 20min, treats that vacuum tightness is evacuated to 4.1 × 10 after arriving assigned temperature
-5back end vacuum tightness is recorded during Pa.
5) open argon bottle, flow control is at 33sccm, 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 0.4Pa.
6) TiB is set
2ceramic target power parameter is: intermediate frequency (MF) 100HKZ, power 300W, dutycycle 80%; Ni metallic target power parameter is: direct current (DC), power 5W; Substrate parameter is: bias voltage 0V, temperature 300 DEG C; After about pre-sputtering 10min, open sample baffle plate, formal sputtering deposits, depositing time: 20min.
7), after deposition terminates, sample baffle plate, target power supply, gas circuit etc. are closed successively; After sample cooling, sampling, namely can obtain the TiB that final product has clad structure
2-Ni film sample.
Embodiment 2:
1) select commercially available purity be 99.9% TiB
2ceramic target and commercially available purity be 99.99% W metal target be raw material; Rapid steel substrate selected by substrate.
2) first carry out the cleaning of matrix, 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) two target magnetic control sputtering systems that this seminar autonomous design is produced are adopted, first after beginning to speak that matrix and target are correctly installed, 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 2.9 × 10
-5during Pa, open sample substrate heating mode, set temperature is 100 DEG C, is incubated 20min, treats that vacuum tightness is evacuated to 3.4 × 10 after arriving assigned temperature
-5back end vacuum tightness is recorded during Pa.
5) open argon bottle, flow control is at 23sccm, 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) 80HKZ, power 100W, dutycycle 90%; Ni metallic target power parameter is: direct current (DC), power 8W; Substrate parameter is: bias voltage-20V, temperature 100 DEG C; After about pre-sputtering 10min, open sample baffle plate, formal sputtering deposits, depositing time: 100min.
7), after deposition terminates, sample baffle plate, target power supply, gas circuit etc. are closed successively; After sample cooling, sampling, namely can obtain the TiB that final product has clad structure
2-Ni film sample.
Embodiment 3:
1) select commercially available purity be 99.9% TiB
2ceramic target and commercially available purity be 99.99% W metal target be raw material; Matrix selects titanium alloy substrate.
2) first carry out the cleaning of matrix, use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning substrate 10min successively respectively, then forced air drying 2h at 80 DEG C, for subsequent use.
3) two target magnetic control sputtering systems that this seminar autonomous design is produced are adopted, first after beginning to speak that matrix and target are correctly installed, 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 2.9 × 10
-5during Pa, open sample substrate heating mode, set temperature is 500 DEG C, is incubated 30min, treats that vacuum tightness is evacuated to 3.2 × 10 after arriving assigned temperature
-5back end vacuum tightness is recorded during Pa.
5) open argon bottle, flow control is at 25sccm, 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 0.9Pa.
6) TiB is set
2ceramic target power parameter is: intermediate frequency (MF) 150HKZ, power 200W, dutycycle 70%; Ni metallic target power parameter is: direct current (DC), power 15W; Substrate parameter is: bias voltage-80V, temperature 500 DEG C; 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 the TiB that final product has clad structure
2-Ni film sample.
Embodiment 4:
1) select commercially available purity be 99.9% TiB
2ceramic target and commercially available purity be 99.99% W metal target be raw material; Copper alloy substrate selected by substrate.
2) first carry out the cleaning of matrix, 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) two target magnetic control sputtering systems that this seminar autonomous design is produced are adopted, first after beginning to speak that matrix and target are correctly installed, 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 1.9 × 10
-5during Pa, without base plate heating.
5) open argon bottle, flow control is at 40sccm, 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) 180HKZ, power 300W, dutycycle 90%; Ni metallic target power parameter is: direct current (DC), power 18W; Substrate parameter is: bias voltage-50V; After about pre-sputtering 10min, open sample baffle plate, formal sputtering deposits, depositing time: 80min.
7), after deposition terminates, sample baffle plate, target power supply, gas circuit etc. are closed successively; After sample cooling, sampling, namely can obtain the TiB that final product has clad structure
2-Ni film sample.
By TiB prepared by above-mentioned technique
2-Ni film typical sample carries out analytical test, obtains following result and data.By the TiB of gained
2-Ni film sample is about 200nm 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 NANOG200 type nano-hardness tester that-Ni film sample adopts American MTS company to produce, recording its hardness is 35GPa.By the TiB of gained
2d8 Advance type x-ray diffractometer (XRD) analytic sample surface crystalline phase composition (Fig. 1) that-Ni film sample adopts German Brooker company to produce, visible prepared TiB
2tiB in-Ni coating
2diffraction peak there is obvious broadening phenomenon, TiB wherein can be inferred
2crystal grain is nano level, and does not have the diffraction peak of obvious W metal in XRD figure spectrum, thus infers that Ni is wherein non-crystalline state.To the TiB of gained
2aXIS ULTRADLD type x-ray photoelectron power spectrum (XPS) that-Ni film sample adopts Japanese Shimadzu Corporation to produce is analyzed, and shows that coat inside Ni content is probably 17%.By the TiB of preparation
2carry out analyzing (Fig. 2) under the Tecnai F20 projection electron microscope (TEM) that-Ni film sample adopts FEI Co. of the U.S. to produce, obviously can find out the TiB of gained
2-Ni film has typical clad structure, TiB
2disperse phase is cell structure, and particle diameter is 5-15nm, and W metal is evenly wrapped in TiB
2particle is outer, and thickness is 1-3nm, and continuous print W metal constitutes continuous print three-dimensional network-like structure simultaneously.In order to prove prepared TiB
2-Ni film has good toughness, friction testing is carried out to described film sample, and carry out microstructure analysis under S-4800 type Scanning Electron microscope (SEM) produced in HIT by cut sample, Photomicrograph (Fig. 3) display of cut, cut surrounding films without significantly bursting apart, peeling phenomenon, surface film material has good toughness.
Claims (6)
1. there is TiB2-nickel film of clad structure, it is characterized in that this TiB
2-Ni film take W metal as external phase, TiB
2crystal grain is that disperse phase In-situ reaction forms, at this TiB
2in-Ni film, W metal is evenly formed the basic boom of film with the continuous cell structure of three-dimensional, and TiB
2crystal grain then fills up inner at cell structure uniformly with particulate state, forms W metal and evenly wraps up TiB
2the coated microstructure of crystal grain, wherein TiB
2content is 60-95at.%, Ni content is 5-40at.%.
2. TiB2 according to claim 1-nickel film, is characterized in that described TiB
2the baseplate material of-Ni film selects silicon single crystal, glass, rapid steel, steel alloy, titanium alloy, copper alloy or nickelalloy.
3. TiB2 according to claim 1-nickel film, is characterized in that described TiB
2tiB in-Ni film
2cellular crystal grain is of a size of 2-80nm, and the thickness of its outer evenly W metal layer of parcel is 0.5-20nm.
4. a preparation method for the TiB2 with the clad structure-nickel film according to claim 1 or 2 or 3, is characterized in that with ceramic target and W metal target for raw material, and adopt magnetic control sputtering system to utilize two target codeposition technique to be prepared, step is:
A) target, substrate are installed;
B) to vacuumize and base plate heating: back end vacuum is lower than 5 × 10
-5pa, the heating temperature range of substrate is room temperature-500 DEG C, and is incubated 20-30min;
C) pass into rare gas element, power supply and substrate parameter are set, build-up of luminance, after pre-sputtering, sputtering sedimentation, wherein TiB
2ceramic target power parameter is: intermediate frequency (MF) 50-200KHZ, power 100-500W, dutycycle 60-90%; Ni metallic target power parameter is: direct current (DC), power 0-20W; Substrate parameter is: bias voltage-100-0V, temperature room temperature-500 DEG C; Pre-sputtering time 8 ~ 15min; Depositing time: 10-120min;
D) deposition terminates, and closes electricity, gas, water route, sampling.
5. preparation method according to claim 4, is characterized in that described step substrate a) needs to use dehydrated alcohol, acetone, dehydrated alcohol ultrasonic cleaning 10 ~ 20min successively before installing, then forced air drying 1 ~ 2h at 70 ~ 90 DEG C.
6. preparation method according to claim 4, is characterized in that described step c) in the rare gas element that passes 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.
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| CN201110418976.7A CN103160777B (en) | 2011-12-15 | 2011-12-15 | Titanium diboride-nickel thin film with coating structure and preparation method thereof |
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| CN103160777B true CN103160777B (en) | 2014-12-17 |
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| CN107012424B (en) * | 2017-03-10 | 2020-09-08 | 广东工业大学 | TiZrB2Hard coating and preparation method and application thereof |
Citations (2)
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|---|---|---|---|---|
| CN1793419A (en) * | 2006-01-04 | 2006-06-28 | 哈尔滨工业大学 | Process for preparing composite thin plate with ceramic particle spreading strengthening intermetallic compound base |
| CN101177742A (en) * | 2007-11-08 | 2008-05-14 | 上海交通大学 | Method for in-situ preparation of TiBO2 reinforced magnesium-based composite material |
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| US7867633B2 (en) * | 2004-06-07 | 2011-01-11 | Colorado School Of Mines | Coatings for glass molding dies and forming tools |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793419A (en) * | 2006-01-04 | 2006-06-28 | 哈尔滨工业大学 | Process for preparing composite thin plate with ceramic particle spreading strengthening intermetallic compound base |
| CN101177742A (en) * | 2007-11-08 | 2008-05-14 | 上海交通大学 | Method for in-situ preparation of TiBO2 reinforced magnesium-based composite material |
Non-Patent Citations (3)
| Title |
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| The effect of composition and process parameters on the erosion resistance of sputtered Ni-TiB2 coatings;James J.Wert etal.;《Wear》;19871231;第116卷;第181－200页 * |
| 吴姚莎等.纳米Ni60-TiB2复合涂层的超音速火焰喷涂制备及600℃循环氧化特性.《材料研究学报》.2011,第25卷(第4期),第391-398页. * |
| 陈志刚等.颗粒弥散强化复相陶瓷.《江苏理工大学学报(自然科学版)》.2000,第21卷(第6期),第90-93页. * |
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