CN103042753B - VC/Co toughening coating layer with nanometer multilayer structure and preparation method thereof - Google Patents
VC/Co toughening coating layer with nanometer multilayer structure and preparation method thereof Download PDFInfo
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- CN103042753B CN103042753B CN201210575224.6A CN201210575224A CN103042753B CN 103042753 B CN103042753 B CN 103042753B CN 201210575224 A CN201210575224 A CN 201210575224A CN 103042753 B CN103042753 B CN 103042753B
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Abstract
The invention discloses a VC/Co toughening coating layer with a nanometer multilayer structure. The coating layer is formed by alternatively depositing VC layers and Co layers; adjacent one VC layer and one Co layer form one double-layer periodic layer; each double-layer periodical layer is 1-88 nm in thickness; the thickness ratio of the VC layer to the Co layer in each double-layer periodic layer is (1.0-3.0):1; and the total thickness of the double-layer periodic layer is 1-5 microns. The invention further discloses a preparation method for the VC/Co toughening coating layer with the nanometer multilayer structure; the method comprises the steps of respectively mounting VC targets and Co targets on medium-frequency cathodes, placing target surfaces perpendicular to a rotary working table, and adopting the magnetron sputtering method to deposit matrixes. At the same time of keeping higher hardness, the VC/Co toughening coating layer with the nanometer multilayer structure improves the toughness, so that the hardness and toughness requirements of protection coating layers and wear-resistant coating layers can be satisfied; and 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 hard coat and preparation method thereof, toughness reinforcing coating of VC/Co particularly relating to a kind of nano-multilayered structures and preparation method thereof, belongs to field of ceramic coatings.
Background technology
The transition metal nitride that hard protection coatings is mainly made up of metallic bond, carbide, boride and the metal oxide etc. be made up of ionic bond are formed, the hardness of these coatings is very high, but their toughness is very low, the toughness improving these coatings is the same important with the hardness improving them, particularly in the application in fretting wear field.
Transition metal Ti, V, W, Ta, Zr, Mo, Cr etc. can react with carbon atom, and generate metal-carbide coating, metal-carbide coating has the advantages that chemical stability is good, fusing point is high, hardness is large, but carbide coating toughness is bad, more crisp.Much research, by a kind of metal poor with C adhesion of compound, can change the structure of metal-carbide coating, thus changes the performance of coating.Now, studying more is imitate the carbide ceramics of block to improve toughness by interpolation the 8th race's element (Fe, Co, Ni etc.), but result is not ideal.As (" Surface & Coatings Technology ", the 206th volume, 583rd ~ 590,2011 years) such as jansson disclose a kind of Ti-C-Me coating, wherein Me is Al, Fe, Ni, Cu, one or more in Pt, but the hardness of this coating only has 7 ~ 18GPa.
Early 1970s, the sandwich construction that Koehler proposes the sizable two kinds of constituent elements of elastic modelling quantity obtains the model of high strong solid, and its thought hinders the generation of dislocation and the effect of motion according to layer material.
Application number be 03129543.6 Chinese patent application disclose a kind of coating of SiC/TiN super hard nano sandwich construction, be made up of on the matrix of metal or pottery TiN layer and SiC layer alternating deposit, the thickness of TiN layer is 4 ~ 50nm, the thickness of SiC layer is 0.4 ~ 0.8nm, nano-multilayer film gross thickness is 2 ~ 4 μm, namely when modulation period is within 50nm, produces superhard effect, the wearability of coating improves, but the toughness of coating is not improved.
Application number be 200910055596.4 Chinese invention patent application disclose a kind of VC/Si
3n
4nano laminated coating and preparation method thereof, described sandwich construction is by VC and Si
3n
4bi-material alternating deposit forms the sandwich construction of nanometer scale, and in its each double-deck cycle, the thickness of VC layer is 2 ~ 8nm, Si
3n
4the thickness of layer is 0.2 ~ 0.9nm, and the gross thickness of coating is 1 ~ 4 μm.This VC/Si
3n
4nano laminated coating adopts double-target radio frequency magnetron sputtering method alternating deposit VC layer and Si on the matrix of metal or pottery
3n
4layer and obtain.This VC/Si
3n
4the hardness of nano laminated coating is higher than 35GPa, and maximum hardness reaches 43GPa, has good hardness, although VC and Si in this coating
3n
4two interfaces form eutectic lattice structure, improve the hardness of coating, but due to VC and Si
3n
4be the hard coat that plasticity index is no more than 0.4, two interfaces form eutectic lattice structure, and reduce the toughness of coating, its coating plasticity index is no more than 0.40.
By doing further retrieval to document and analyzing, also do not find the VC/Co coating of nano-multilayered structures, do not find to have excellent toughening effect and the hardness toughness reinforcing coating more than the VC/Co nano-multilayered structures of 15GPa yet.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of toughness reinforcing coating of VC/Co of nano-multilayered structures, while ensureing that coating has excellent hardness, improve the toughness of coating, thus improve the abrasion resistance properties of coating.
The present invention is achieved by the following technical solutions, the toughness reinforcing coating of VC/Co of nano-multilayered structures of the present invention is formed by VC layer and Co layer alternating deposit, adjacent one deck VC layer and one deck Co layer form a double-deck cycle layer, the thickness of each double-deck cycle layer is 1 ~ 88nm, in each double-deck cycle layer, the Thickness Ratio of VC layer and Co layer is 1.0 ~ 3.0:1, and the gross thickness of the toughness reinforcing coating of VC/Co of nano-multilayered structures is 1 ~ 5 μm.
For single layer structure, when by external force, metal Co individual layer consumes most of energy by detrusion, reduces stress and concentrates, not easily crack initiation, and ceramic phase VC due to plasticity very poor, can not be relaxed concentrated stress, and serious distortion appears at the defective locations of coating, and cause cracking further, crack initiation, expanding subsequently and assembling becomes lead crack.But in the toughness reinforcing coating of the VC/Co of nano-multilayered structures of the present invention, when applying applied external force, Co monofilm relaxes stress, not easily crack initiation by detrusion consumed energy, improves the toughness of coating.Meanwhile, on two-phase interface, Metal Phase Co segregation is on crystal boundary, inhibits growing up of VC crystal grain, and the toughness of coating is relative with hardness to be improved.
The uniformity of coating, hardness improves along with the reduction of double-deck cycle layer thickness, but along with the reduction of double-deck cycle layer thickness, the toughness reinforcing coating of VC/Co of nano-multilayered structures of the present invention becomes difficulty with the difference of the coating with homogeneous texture, but, after the thickness of double-deck cycle layer is more than 88nm, shortcoming in coating in single layer structure just becomes obvious, while the hardness of coating and toughness reduce, its anti-wear performance reduces, the preferred value of the double-deck cycle layer be made up of adjacent one deck VC layer and one deck Co layer is 3 ~ 60nm, namely the thickness of each double-deck cycle layer is preferably 3 ~ 60nm.
As preferably, the thickness of each double-deck cycle layer is all equal, namely with a modulation period to VC layer and Co layer alternating deposit, double-deck cycle layer is uniformly distributed, greatly can improves toughness and the hardness of coating.
From the hardness of embodiment 2,3,8,9 and 11 and the characterization data of toughness, the thickness of each double-deck cycle layer is 6 ~ 24.9nm, in each double-deck cycle layer, the Thickness Ratio of VC layer and Co layer is 2.0 ~ 3.0:1, and the thickness of each double-deck cycle layer is all equal, make the toughness reinforcing coating of the VC/Co of nano-multilayered structures of the present invention have excellent hardness and toughness, the requirement of hard wear-resistant coating can be met well.
Present invention also offers a kind of preparation method of the toughness reinforcing coating of VC/Co of above-mentioned nano-multilayered structures, comprise: VC target and Co target are arranged on intermediate frequency negative electrode respectively, target surface is perpendicular to rotary table, matrix is arranged on rotary table, by regulating the rotating speed of rotary table and the sputtering power of target, adopt magnetically controlled sputter method, matrix is deposited, obtains the toughness reinforcing coating of VC/Co of nano-multilayered structures.
The present invention selects the method for magnetron sputtering to prepare the toughness reinforcing coating of VC/Co of nano-multilayered structures, during due to magnetron sputtering, ion beam is splashed on matrix in pencil by target surface, this kind of method can avoid the premixed of two kinds of retes in deposition process, obtain the toughness reinforcing coating of VC/Co of the nano-multilayered structures with clear interface, it be simple to operate, controllability good, easy to implement.
As preferably, before deposition, the background pressure of vacuum chamber is less than or equal to 5 × 10
-5pa, namely the background pressure of vacuum chamber is less than or equal to 5 × 10
-5after Pa; pass into the protective gas such as argon gas; the collision in sputter procedure between sputtering particle and gas molecule can be reduced; gas molecule in deposition process can be reduced enter in coating and become impurity simultaneously, improve the density of the toughness reinforcing coating of VC/Co of nano-multilayered structures of the present invention, purity, sedimentation rate and the adhesive force with matrix.
During deposition, depositing temperature is 200 DEG C ~ 400 DEG C, and deposition pressure is 0.3Pa ~ 1.0Pa, and under this sputtering parameter, the toughness reinforcing coating structure of VC/Co of the nano-multilayered structures of the present invention that deposition can be made to obtain is fine and close.
In the Sputtering power density of VC target and Co target and the toughness reinforcing coating of VC/Co of nano-multilayered structures of the present invention, the thickness of double-deck cycle layer is closely related, and the structure of the toughness reinforcing coating of the VC/Co that can affect nano-multilayered structures of the present invention, as preferably, during deposition, VC target Sputtering power density is: 4.0 ~ 6.5W/cm
2, Co target Sputtering power density is: 0.5 ~ 0.8W/cm
2, now, the requirement of the hardness of the toughness reinforcing coating of the VC/Co of nano-multilayered structures of the present invention and tough sexual satisfaction protective coating and wear-resistant coating can be made.Meanwhile, the rotating speed of rotary table also determines the thickness of double-deck cycle layer, and as preferably, during deposition, the rotating speed of rotary table is 0.5 ~ 4.0 rev/min (r/min).
Compared with prior art, the present invention has the following advantages:
One, the toughness reinforcing coating of the VC/Co of nano-multilayered structures provided by the present invention, while increase coating toughness, the hardness of coating can reach more than 15GPa, can meet the requirement of protective coating and wear-resistant coating toughness and hardness, has very large using value;
Two, the preparation method of the toughness reinforcing coating of the VC/Co of nano-multilayered structures provided by the present invention, it is workable, controllability good, be easy to suitability for industrialized production, has good economic benefit.
Accompanying drawing explanation
Fig. 1 is the structural representation of the toughness reinforcing coating of VC/Co of nano-multilayered structures of the present invention, and wherein 1 is VC layer, and 2 is Co layer;
Fig. 2 is the device schematic diagram of the toughness reinforcing coating of VC/Co preparing nano-multilayered structures of the present invention, and wherein, 3 is matrix, and 4 is anode, and 5,6 is the VC target and Co target that are connected with intermediate frequency negative electrode;
In Fig. 3, the impression figure of a VC coating that () is comparative example, the impression figure of b VC/Co coating that () is the nano-multilayered structures of embodiment 2, the impression figure of c VC/Co coating that () is the nano-multilayered structures of embodiment 6, the impression figure of the VC/Co coating that (d) is the nano-multilayered structures of embodiment 7.
Detailed description of the invention
The equipment of deposited coatings
Fig. 2 is the device schematic diagram of the preparation method of the toughness reinforcing coating of VC/Co implementing nano-multilayered structures of the present invention, as shown in Figure 2, this device comprises anode 4, the rotary table be connected with anode 4, the VC target 5 be connected with intermediate frequency negative electrode, Co target 6, VC target 5, Co target 6, perpendicular to the table top of rotary table, rotary table are provided with matrix 3.Adopt magnetron sputtering technique, sputter VC by the VC target 5 be connected with intermediate frequency negative electrode, Co target 6 sputters Co, obtains the toughness reinforcing coating of VC/Co of nano-multilayered structures.
The method of deposited coatings
The kind of matrix
The indices of crystallographic plane that employing is of a size of 20mm × 20mm × 0.5mm are the silicon chip of (100).
The preparation method of comparative example and embodiment 1 ~ 11 floating coat:
First to matrix 3(and silicon chip) clean, first matrix 3 being put into model that Borer company produces is the ultrasonic cleaning 3 minutes at the temperature of 60 DEG C of the washing agent of HT1401, then putting into model that Borer company produces is the ultrasonic cleaning 3 minutes at the temperature of 50 DEG C of the washing agent of HT1233,0.5 minute is cleaned again the deionized water for ultrasonic of 45 DEG C, the vacuum drying chamber finally matrix 3 after cleaning being put into 95 DEG C toasts 3 minutes, puts on the rotary table of vacuum chamber after oven dry.
VC target 5 and Co target 6 are arranged on intermediate frequency negative electrode respectively, vacuum chamber is vacuumized, and matrix is heated to required depositing temperature, when the background pressure (back end vacuum) of vacuum chamber reaches required pressure, pass into Ar gas, pressure is adjusted to required deposition pressure, regulate the power density of VC target 5 and the power density of Co target 6 and the rotating speed of rotary table simultaneously, to matrix 3 sputtering sedimentation, the VC/Co coating of the thickness obtaining comparative example to be the VC coating of 2 μm and embodiment 1 ~ 11 thickness the be nano-multilayered structures of 2 μm, experiment parameter in magnetron sputtering process and the physical property of coating obtained as shown in table 1.
Table 1
From the results shown in Table 1, the toughness reinforcing coating of VC/Co of the nano-multilayered structures in the embodiment of the present invention is compared to the VC coating in comparative example, along with the increase of the double-deck cycle layer thickness of VC/Co, hardness decreases, but its hardness is all at more than 15GPa, the requirement of hardness wear-resistant coating can be met completely.From the hardness of embodiment 2,3,8,9 and 11 and the characterization data of toughness, VC coating in hardness and comparative example is basically identical, but toughness has had and has improved greatly, make the toughness reinforcing coating of the VC/Co of nano-multilayered structures of the present invention have excellent hardness and toughness, the requirement of hard wear-resistant coating can be met well.
As shown in Figure 1, the toughness reinforcing coating of VC/Co for nano-multilayered structures of the present invention, formed by VC layer 1 and Co layer 2 alternating deposit, adjacent one deck VC layer 1 and one deck Co layer 2 form a double-deck cycle layer, the thickness of each double-deck cycle layer is 1 ~ 88nm, in each double-deck cycle layer, VC layer 1 is 1.0 ~ 3.0:1 with the Thickness Ratio of Co layer 2, and the gross thickness of the toughness reinforcing coating of VC/Co of nano-multilayered structures is 1 ~ 5 μm.
Fig. 3 is the impression figure of coating under the pressure of 3N, the impression figure of the VC coating that figure (a) is comparative example, figure (b), (c), (d) are respectively the impression figure of the VC/Co coating of the nano-multilayered structures of embodiment 2, embodiment 6 and embodiment 7, as can be seen from figure (a), obvious crackle is there is in simple VC coating under the pressure of 3N, and it is serious to angular direction Crack Extension, a small amount of indentation crack is had in figure (b) impression, to the expansion of angular direction flawless, without obvious indentation crack, without obvious running crack in figure (c), (d).This illustrates that the toughness of coating obtains large increase relative to simple VC coating toughness.
The present invention adopts following experimental technique to assess the toughness reinforcing coating of VC/Co of the nano-multilayered structures obtained in embodiment.
The measurement of hardness
The model adopting American MTS to produce is the hardness that NANO G200 nano-hardness tester measures each film system, its configuration tetrahedron Berkvich pressure head, by setting compression distance (100nm), load changes with compression distance, and each sample is averaged after measuring 6 matrix dots.
The measurement of impression
Employing model is that the microhardness testers of HV-1000 carry out micro indentation test to sample.By being applied to the pressure (3N) on pressure head, observe length, the crackle that more different sample produces and the spread scenarios of the crackle that impression produces.
The measurement of plasticity index
The model adopting American MTS to produce is that NANO G200 nano-hardness tester measures coating plasticity and elastic deformation, its configuration tetrahedron Berkvich pressure head, by setting compression distance (100nm), load changes with compression distance, and each sample is averaged after measuring 6 matrix dots.According to the plastic deformation obtained 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 (6)
1. the toughness reinforcing coating of the VC/Co of a nano-multilayered structures, it is characterized in that, formed by VC layer and Co layer alternating deposit, adjacent one deck VC layer and one deck Co layer form a double-deck cycle layer, the thickness of each double-deck cycle layer is all equal, the thickness of each double-deck cycle layer is 6 ~ 24.9nm, and in each double-deck cycle layer, the Thickness Ratio of VC layer and Co layer is 2.0 ~ 3.0:1, and the gross thickness of the toughness reinforcing coating of VC/Co of nano-multilayered structures is 1 ~ 5 μm.
2. the preparation method of the toughness reinforcing coating of the VC/Co of nano-multilayered structures according to claim 1, it is characterized in that, comprise: VC target and Co target are arranged on intermediate frequency negative electrode respectively, target surface is perpendicular to rotary table, matrix is arranged on rotary table, by regulating the rotating speed of rotary table and the sputtering power of VC target and Co target, adopts magnetically controlled sputter method, matrix is deposited, obtains the toughness reinforcing coating of VC/Co of nano-multilayered structures.
3. the preparation method of the toughness reinforcing coating of the VC/Co of nano-multilayered structures according to claim 2, is characterized in that, before deposition, the background pressure of vacuum chamber is less than or equal to 5 × 10
-5pa.
4. the preparation method of the toughness reinforcing coating of the VC/Co of nano-multilayered structures according to claim 2, is characterized in that, during deposition, depositing temperature is 200 DEG C ~ 400 DEG C, and deposition pressure is 0.3Pa ~ 1.0Pa.
5. the preparation method of the toughness reinforcing coating of the VC/Co of nano-multilayered structures according to claim 2, is characterized in that, during deposition, VC target Sputtering power density is: 4.0 ~ 6.5W/cm
2, Co target Sputtering power density is: 0.5 ~ 0.8W/cm
2.
6. the preparation method of the toughness reinforcing coating of the VC/Co of nano-multilayered structures according to claim 2, is characterized in that, during deposition, the rotating speed of described rotary table is 0.5 ~ 4.0 rev/min.
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| CN101618615A (en) * | 2009-07-30 | 2010-01-06 | 上海工具厂有限公司 | VC/Si3N4 nano laminated coating and preparation method thereof |
| US20110135897A1 (en) * | 2009-12-06 | 2011-06-09 | Iscar, Ltd. | Coated Article and Method for Making a Coated Article |
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| KR20100048504A (en) * | 2008-10-31 | 2010-05-11 | 전북대학교산학협력단 | Properties and method for making nanostructured metal carbides-metal hard materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462386A (en) * | 2007-12-21 | 2009-06-24 | 山特维克知识产权股份有限公司 | Coated cutting tool and a method of making a coated cutting tool |
| CN101618615A (en) * | 2009-07-30 | 2010-01-06 | 上海工具厂有限公司 | VC/Si3N4 nano laminated coating and preparation method thereof |
| US20110135897A1 (en) * | 2009-12-06 | 2011-06-09 | Iscar, Ltd. | Coated Article and Method for Making a Coated Article |
Non-Patent Citations (1)
| Title |
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| 杨修春等编著.磁控阴极溅射法.《新型建筑玻璃》.中国电力出版社,2009,第107-112页. * |
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