CN102864413B - V-C-Co flexible coating with nano composite structure and preparation method of V-C-Co flexible coating - Google Patents
V-C-Co flexible coating with nano composite structure and preparation method of V-C-Co flexible coating Download PDFInfo
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Abstract
The invention discloses a V-C-Co flexible coating with a nano composite structure. The V-C-Co flexible coating comprises the following elements in percent by weight: 33.9-70.0 percent of V, 15.1-23.0 percent of C and 7.0-45.0 percent of Co, and belongs to the field of ceramic coatings. The invention also discloses a preparation method of the V-C-Co flexible coating with the nano compound structure. The preparation method comprises the steps of: installing a VC target on a medium-frequency cathode, installing a Co target on a direct current cathode, and sputtering a matrix by using a magnetic control sputtering method for depositing the V-C-Co flexible coating with the nano compound structure. The V-C-Co flexible coating with the nano compound structure, prepared by adopting the method, has the characteristic s of high hardness and high flexibility, has plastic index being above 0.45 and hardness being above 15GPa, and can meet the requirements of high hardness and high flexibility of a protective coating and a wear-resistant coating. The preparation method has the advantages of strong operability, good controllability, and easiness in industrial production.
Description
Technical field
The present invention relates to a kind of toughness hard coat and preparation technology thereof, relate in particular to V-C-Co coating of a kind of nano combined mechanism and preparation method thereof, belong to field of ceramic coatings.
Background technology
Hard protection coatings is mainly to form transition metal nitride, carbide, boride and the metal oxide that is made up of ionic linkage etc. forms by metallic bond, the hardness of these coatings is very high, but their toughness is very low, the toughness that improves these coatings is the same important with the hardness that improves them, particularly in the application in frictional wear field.
M.Misina utilizes non-balance magnetically controlled sputter equipment to prepare Ti-N-Ni coating (" Surface and Coating Technology ", the 110th volume, 168～172 pages, 1998), metal Ni forms the metal Ni phase of FCC structure on the crystal boundary of TiN with absolute version segregation, coating just becomes the nano-composite coating by metal Ni phase and TiN phase composite like this, still, although the toughness of this kind of coating is significantly improved, coating highest hardness only has 10.5GPa.
Transition metal Ti, V, W, Ta, Zr, Mo, Cr etc. can react with carbon atom, generate metal-carbide coating, and metal-carbide coating has the advantages that chemical stability is good, fusing point is high, hardness is large, and still, carbide coating toughness is bad, more crisp.Much research, by the poor metal of compound a kind of and C bonding force, can change its structure, thereby changes the performance of coating.Now, studying more is to imitate the carbide ceramics of block to improve toughness by adding the 8th family's element (Fe, Co, Ni etc.), but result is not ideal.As (" Surface & Coatings Technology " such as jansson, the 206th volume, 583rd～590,2011) announce a kind of Ti-C-Me coating, wherein Me is Al, Fe, Ni, Cu, one or more in Pt, but the hard of this coating only has 7～18GPa.
WC coating fusing point is high, hardness is large, frictional coefficient is low, become the main component of hard alloy coating, the strength of materials such as Co, Ni is suitable, there is certain plasticity, with WC combination, make the existing high hardness of hard coat, toughness also improves simultaneously, patent CN102418065A has announced a kind of composite metal carbide wear-resistant coating, and this coating is formed by hypersonic flame spraying by binding agent coating carbide and carbide, and the Vickers' hardness of coating is 1200～1800kg/mm
2but the hardness of this kind of coating is low, void content is high.
By document being done to further retrieval and being analyzed, also do not find the V-C-Co coating of nano composite structure, do not find the V-C-Co coating that its plasticity index exceedes 0.45, hardness exceedes 15GPa yet.
Summary of the invention
The invention provides V-C-Co (vanadium-carbon-cobalt) flexible coating of a kind of nano composite structure and preparation method thereof, this coating has the feature of high rigidity and high tenacity simultaneously, can meet the requirement of protective coating and wear-resistant coating.
A V-C-Co flexible coating for nano composite structure, by weight percentage, component is:
V 33.9～70.0％
C 15.1～23％
Co 7.0～45.0％。
In the present invention, described V-C-Co flexible coating is compared with common vanadium carbide coating, add a certain amount of Co, the Co adding can improve the toughness of coating, plasticity index is not less than 0.45, and meanwhile, the hardness of coating also exceedes 15GPa, therefore, the V-C-Co flexible coating in the present invention can meet the requirement of protective coating and wear-resistant coating.
In order further to improve the toughness of described V-C-Co flexible coating, ensure again the hardness of coating simultaneously, by weight percentage, component is preferably:
V 45.9～65.7％
C 18.1～22.2％
Co 12.1～36.0％。
As preferably, described V-C-Co flexible coating comprises VC phase and Co phase; Described VC has crystalline structure mutually, formed by VC crystal grain, described VC be scattered in mutually Co mutually in, described Co is non-crystal structure mutually, in the present invention, Co is gathered on the crystal boundary of VC crystal grain, forms stronger Co-VC chemical bond, has suppressed growing up of VC crystal grain, the Co of amorphous phase has good plastic deformation ability simultaneously, in the toughness that ensures to have improved in coating has higher hardness coating.
As preferably, the particle diameter of described VC crystal grain is 5～15nm, the distance of adjacent two VC crystal grain is 1～5nm, and the particle diameter of VC crystal grain and distance affects hardness and the toughness of described V-C-Co flexible coating, and the increase of described distance can make the toughness of described V-C-Co flexible coating increase.
The V-C-Co flexible coating of described nano composite structure can form by methods known in the art, comprise physical vapor deposition (PVD) and chemical vapour deposition (CVD), consider the reasons such as the sticking power of coating, preferably consider PVD, PVD need not be heated to body material the needed temperature of CVD, therefore,, in the process of deposition, reduced the risk that body material worsens.
The present invention also provides a kind of preparation method of V-C-Co flexible coating of above-mentioned nano composite structure, comprise: VC target is arranged on intermediate frequency negative electrode, Co target is arranged on direct current negative electrode, adopt magnetically controlled sputter method, matrix is deposited, obtain described V-C-Co flexible coating, the present invention selects the method for magnetron sputtering to prepare nano composite structure V-C-Co flexible coating, workable, controllability good, easy to implement.
As preferably, when deposition, depositing temperature is 200 DEG C～400 DEG C, and deposition pressure is 0.3Pa～1.0Pa, under this sputtering parameter, and the V-C-Co flexible coating compact structure that can make deposition obtain.
When deposition, the background pressure of described vacuum chamber is less than or equal to 5 × 10
-5pa, can reduce the collision between sputtering particle and gas molecule in sputter procedure, can reduce in deposition process gas molecule simultaneously and enter in coating and become impurity, improve the density, purity, sedimentation rate of the V-C-Co coating of nano composite structure of the present invention and the sticking power with substrate.
In the Sputtering power density of VC target and Co target and described V-C-Co flexible coating, the ratio of V and Co is closely related, and can affect the structure of described V-C-Co flexible coating, and as preferably, when deposition, VC target Sputtering power density is: 2.5～6.2W/cm
2, Co target Sputtering power density is: 0.05～0.5W/cm
2, now, can make the described hardness of V-C-Co flexible coating and the requirement of tough sexual satisfaction protective coating and wear-resistant coating.
Compared with prior art, the present invention has the following advantages:
(1) the V-C-Co flexible coating of nano composite structure provided by the present invention, with the feature of high rigidity, high tenacity, its plasticity index is more than 0.45, more than hardness reaches 15GPa, can meet the requirement of protective coating and wear-resistant coating high rigidity and high tenacity, there is very large using value;
(2) preparation method of the V-C-Co flexible coating of while nano composite structure provided by the present invention, it is workable, controllability good, be easy to suitability for industrialized production, has good economic benefit.
Brief description of the drawings
Fig. 1 is the device schematic diagram of the V-C-Co flexible coating of preparation nano composite structure of the present invention;
Fig. 2 is the TEM figure of the V-C-Co flexible coating that makes of embodiment 6;
Fig. 3 is the XRD figure of the V-C-Co coating that makes of comparative example, embodiment 2, embodiment 6 and embodiment 7;
In Fig. 4, (a) the SEM sectional view of the V-C-Co coating that part makes for comparative example, (b) the SEM sectional view of the V-C-Co flexible coating that part makes for embodiment 2, (c) the SEM sectional view of the V-C-Co flexible coating that part makes for embodiment 6, the SEM sectional view of the V-C-Co flexible coating that (d) part makes for embodiment 7.
Embodiment
The equipment of deposited coatings
Fig. 1 is the device of implementing the preparation method of the V-C-Co flexible coating of nano composite structure of the present invention, as shown in Figure 1, matrix 2 that this device comprises direct current anode 1, be connected with direct current anode 1, intermediate frequency negative electrode 3, direct current negative electrode 4, the VC target 5 being connected with intermediate frequency negative electrode 3, the Co target 6 and the baffle plate 7 that are connected with direct current negative electrode 4, adopt magnetron sputtering technique, the VC target 5 sputter VC that connect by intermediate frequency negative electrode 3, the Co target 6 splash-proofing sputtering metal Co that direct current negative electrode 4 connects, the V-C-Co flexible coating of generation nano composite structure.
The method of deposited coatings
The kind of matrix
Employing is of a size of the rapid steel testing plate of 20 × 20 × 2mm.
The preparation method of V-C-Co coating in embodiment 1～11 and comparative example:
First rapid steel testing plate is cleaned, the ultrasonic cleaning 3 minutes at the temperature of 60 DEG C of first matrix to be put into model that Borer company produces be HT1401 washing composition, then the ultrasonic cleaning 3 minutes at the temperature of 50 DEG C of to put into model that Borer company produces be HT1233 washing composition, clean 0.5 minute the deionized water for ultrasonic of 45 DEG C again, the vacuum drying oven of finally matrix after cleaning being put into 95 DEG C toasts 3 minutes, puts on the rotatable base frame 2 of vacuum chamber after oven dry.
VC target is arranged on intermediate frequency negative electrode, and Co target is arranged on direct current negative electrode, and VC target and Co target are by baffle plate 7 and matrix isolation.Cavity 8 is vacuumized, and matrix is heated to required depositing temperature, when vacuum tightness reaches 5 × 10
-5in Pa time, pass into Ar gas, pressure is adjusted to required deposition pressure, apply bias voltage by grid bias power supply to matrix, regulate the power density of VC target and the power density of Co target simultaneously, to matrix sputtering sedimentation, obtaining thickness is the V-C-Co coating of the nano composite structure of 1.5 μ m, and the physicals of the experiment parameter in magnetron sputtering process and the coating obtaining is as shown in table 1.
From the results shown in Table 1, the V-C-Co flexible coating of the nano composite structure in the embodiment of the present invention is than the coating in comparative example, although hardness decreases, but plasticity index is improved significantly, wherein, the plasticity index of the coating that embodiment 11 obtains, by original 0.4, rises to 0.67, and this toughness that indicates coating strengthens.
Fig. 2 is the TEM figure of the coating that makes of embodiment 6, Fig. 2 shows, this coating is made up of the VC phase of crystalline structure and the Co external phase of non-crystal structure, the VC of each crystalline structure is wrapped up by the Co external phase of non-crystal structure, Co is gathered on the crystal boundary of VC crystal grain, forms stronger Co-VC chemical bond, has suppressed growing up of VC crystal grain, in coating, the mean sizes of VC crystal grain is 5～15nm, and the distance of adjacent two VC intergranules is 1～5nm.
Fig. 4 is the SEM sectional view of comparative example, embodiment 2, embodiment 6, embodiment 7, as can be seen from Figure 4, although adding coating after Co is still columnar structure, but do not add the VC coating of Co than Fig. 4 (a), the coating column compact structure of Fig. 4 (b) nano composite structure, more trends towards filamentary structure.
The present invention adopts structural parameter and the physicals of the V-C-Co flexible coating of the nano composite structure obtaining in following experimental technique assessment embodiment.
The composition of coating
Adopt EDS to measure the composition that each film is, its configuration EDAX Si (Li) probe, calibrates by ZAF, and the selected area of each sample is not less than 40mm
2region, measures the mean value of its composition.
The crystalline structure of coating
Adopt German Bruker D8 Advance diffractometer, utilize the incident of Cu K alpha-ray, X-ray tube is controlled at 40KV and 40mA, measures the crystalline structure that each film is, utilizes nickel filter to filter out K
βray, it is 20 °～80 ° that search angle is set.
The measurement of hardness
The model that adopts American MTS to produce is that NANO G200 nano-hardness tester is measured hardness and the Young's modulus that each film is, its configuration tetrahedron Berkvich pressure head, by setting compression distance (100nm), load changes with compression distance, after 6 matrix dots of each sample measurement, averages.
The measurement of plastic coefficient
The model that adopts American MTS to produce is that NANO G200 nano-hardness tester is measured coating plasticity and elastic deformation, its configuration tetrahedron Berkvich pressure head, by setting compression distance (100nm), load changes with compression distance, after 6 matrix dots of each sample measurement, averages.According to the plastic deformation obtaining and elastic deformation, utilize formula (1) computational plasticity index.
Wherein δ
hfor plasticity index, ε
pfor plastic deformation, ε
efor elastic deformation, ε=ε
p+ ε
e.
Claims (7)
1. a V-C-Co flexible coating for nano composite structure, is characterized in that, by weight percentage, component is:
V 39.9～70.0%
C 15.1～23.0%
Co 7.0～45.0%。
2. the V-C-Co flexible coating of nano composite structure according to claim 1, is characterized in that, by weight percentage, component is:
V 45.9～65.7%
C 18.1～22.2%
Co 12.1～36.0%。
3. the V-C-Co flexible coating of nano composite structure according to claim 1 and 2, is characterized in that, described V-C-Co flexible coating comprises VC phase and Co phase;
Described VC has crystalline structure mutually, formed by VC crystal grain, described VC be scattered in mutually Co mutually in;
Described Co is non-crystal structure mutually.
4. the V-C-Co flexible coating of nano composite structure according to claim 3, is characterized in that, the particle diameter of described VC crystal grain is 5～15nm, and the distance of adjacent two VC crystal grain is 1～5nm.
5. according to the preparation method of the V-C-Co flexible coating of the nano composite structure described in claim 1～4 any one, it is characterized in that, comprise: VC target is arranged on intermediate frequency negative electrode, Co target is arranged on direct current negative electrode, adopt magnetically controlled sputter method, matrix is deposited, obtain described V-C-Co flexible coating.
6. the preparation method of the V-C-Co flexible coating of nano composite structure according to claim 5, is characterized in that, when deposition, depositing temperature is 200 DEG C～400 DEG C, and deposition pressure is 0.3Pa～1.0Pa.
7. the preparation method of the V-C-Co flexible coating of nano composite structure according to claim 5, is characterized in that, when deposition, VC target Sputtering power density is: 2.5～6.2W/cm
2, Co target Sputtering power density is: 0.05～0.5 W/cm
2.
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| CN101307421A (en) * | 2008-06-06 | 2008-11-19 | 北京工业大学 | Method for preparing WC-Co metal-ceramic coating of superfine structure |
| CN101580941A (en) * | 2009-06-30 | 2009-11-18 | 北京科技大学 | Method for preparing WC-Co hard coating |
| CN102031516A (en) * | 2010-12-21 | 2011-04-27 | 上海工程技术大学 | Method for preparing Ni-based nano WC/Co composite coating with gradient function |
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| CN101307421A (en) * | 2008-06-06 | 2008-11-19 | 北京工业大学 | Method for preparing WC-Co metal-ceramic coating of superfine structure |
| CN101580941A (en) * | 2009-06-30 | 2009-11-18 | 北京科技大学 | Method for preparing WC-Co hard coating |
| CN102031516A (en) * | 2010-12-21 | 2011-04-27 | 上海工程技术大学 | Method for preparing Ni-based nano WC/Co composite coating with gradient function |
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