CN109628896A - A kind of gradient-structure TiAlSiYN polynary nanometer coating and preparation method thereof - Google Patents
A kind of gradient-structure TiAlSiYN polynary nanometer coating and preparation method thereof Download PDFInfo
- Publication number
- CN109628896A CN109628896A CN201910042017.6A CN201910042017A CN109628896A CN 109628896 A CN109628896 A CN 109628896A CN 201910042017 A CN201910042017 A CN 201910042017A CN 109628896 A CN109628896 A CN 109628896A
- Authority
- CN
- China
- Prior art keywords
- content
- coating
- alloy target
- target
- tialsiyn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 103
- 239000011248 coating agent Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 57
- 238000000151 deposition Methods 0.000 claims abstract description 48
- 239000011159 matrix material Substances 0.000 claims abstract description 33
- 230000008021 deposition Effects 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 238000005477 sputtering target Methods 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims description 97
- 229910045601 alloy Inorganic materials 0.000 claims description 96
- 239000000758 substrate Substances 0.000 claims description 63
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- 239000002103 nanocoating Substances 0.000 claims description 27
- 238000004544 sputter deposition Methods 0.000 claims description 27
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 16
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 15
- 238000007733 ion plating Methods 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910010037 TiAlN Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910008482 TiSiN Inorganic materials 0.000 claims description 3
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000000992 sputter etching Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract description 10
- 238000010891 electric arc Methods 0.000 abstract description 6
- 239000010936 titanium Substances 0.000 abstract 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 5
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 25
- 238000001514 detection method Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- 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
- C23C14/0021—Reactive sputtering or evaporation
-
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
Landscapes
- 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
Gradient-structure TiAlSiYN polynary nanometer coating disclosed by the invention is made of three the different internal layer of ingredient, middle layer, outer layer sublayers, Al content is successively decreased in each sublayer from the inner to the outer, is followed successively by (15 ~ 20) at.%, (10 ~ 15) at.%, (7 ~ 10) at.%；Ti content is incremented by, and is followed successively by (28 ~ 32) at.%, (32 ~ 36) at.%, (36 ~ 40) at.%；Si content is (1 ~ 3) at.%, Y content < 0.1at.% in each sublayer, remaining as N.The invention also discloses preparation methods, deposit a period of time first with the titanium aluminium electric arc target, titanium silicon electric arc target and yttrium sputtering target of high aluminium content；Be then shut off the titanium aluminium target of high aluminium content, in opening aluminium content titanium aluminium electric arc target, continue deposition a period of time；The titanium aluminium electric arc target of the titanium aluminium target of aluminium content, opening low-aluminum-content, terminates after redeposited a period of time in finally closing.Gradient-structure TiAlSiYN polynary nanometer coating of the invention is firmly combined with matrix, while having good toughness and antifriction performance, and preparation method controllability is good, easy to implement, is suitble to industrialized production and application.
Description
Technical Field
The invention belongs to the technical field of surface coatings of cutting tools, and particularly relates to a preparation method of a gradient structure TiAlSiYN multi-element nano coating.
Background
The preparation of a hard coating on the surface of a cutting tool not only can further enhance the hardness of the surface of the tool and resist abrasion, but also the coating can often hinder thermal diffusion and chemical diffusion. The TiAlSiN coating is a quaternary coating developed by adding a small amount of Si atoms on the basis of the TiAlN ternary coating. The Si element is usually in the form of net nc-Si in the coating4N3The continuous amorphous phase breaks through the mode that the coating grows according to a columnar structure, limits the growth of the wrapped TiAlN grains, refines the grains, and also serves as an interface phase to hinder dislocation motion and crack propagation, so that the TiAlSiN coating often has high hardness and even has a superhard effect. The TiAlSiN coating is also characterized in that Si element and O element are combined to generate compact SiO at high temperature2The oxide film can block and slow down the continuous diffusion of the O element in the environment to the coating, so the TiAlSiN coating also has good high-temperature oxidation resistance. The TiAlSiN coating has high hardness and high oxidation resistance, so that the TiAlSiN coating has potential application value and is particularly suitable for high-speed cutting, dry cutting and precise cutting occasions.
Currently, the TiAlSiN coating is toughened and modified, so that the TiAlSiN coating has the comprehensive performance of being hard and tough and being well combined with a substrate, and the method is an important way for exerting the performance advantages of the TiAlSiN coating. Researches prove that other component elements are doped in the TiAlSiN quaternary coating, so that the toughness of the TiAlSiN coating can be effectively improved. J. Shi et al (doi: 10.1016/j. surfcoat.2011.12.027) report that a Cu block is embedded in a TiAlSi alloy target material, a Cu-doped TiAlSiCuN five-membered coating is prepared by co-sputtering TiAlSi alloy and Cu, after the Cu is doped, the coating is obviously softened, when about 1at.% of Cu is added into the coating, the hardness of the coating is reduced to 23GPa, and the hardness of the TiAlCuN five-membered coating is continuously reduced along with the increase of the content of the added Cu atoms; the Cu element can enhance the combination of the coating and the substrate, compared with the TiAlSiN coatingThe limit load is 32N, and the critical load of the TiAlSiCuN coating can reach 50N. The report does not directly compare the change of the toughness of the coating before and after doping, and the Cu element has good toughening effect from the aspect of hardness change alone, but the sputtering coating method adopted by the report has low coating deposition efficiency, and the homogeneity and stability of the coating components are difficult to ensure by using the mosaic target. Y is a rare element with active chemical property, the high-temperature performance of the coating can be improved by doping the rare element in the coating, and T, Mori et al (doi: 10.1016/j. surfcoat.2012.10.050) utilize Ti63Al27Si10And Cr45Al53Y2The TiAlSiN/CrAlYN nano multilayer coating with different modulation periods is prepared by arc ion plating of two targets, and the hardness of the coating is about 37GPa, which is consistent with that of a TiAlSiN single-layer coating. Similarly, from the aspect of hardness change alone, no toughening phenomenon is found when the TiAlSiN coating is doped with two elements of Cr and Y.
Disclosure of Invention
The invention aims to provide a gradient structure TiAlSiYN multi-element nano coating aiming at the problems in the prior art.
The invention also aims to provide a preparation method of the gradient structure TiAlSiYN multi-component nano coating.
The gradient-structure TiAlSiYN multi-element nano coating provided by the invention is a five-element coating composed of five elements of Ti, Al, Si, Y and N, the coating structure is composed of an inner sublayer, a middle sublayer and an outer sublayer which are different in components, the Al content in the sublayers from the inner sublayer to the outer sublayer is sequentially reduced, the Ti content is sequentially increased, the Al content in the inner sublayer is (15-20) at.%, the Ti content is (28-32) at.%, the Al content in the middle sublayer is (10-15) at.%, the Ti content is (32-36) at.%, the Al content in the outer sublayer is (7-10) at.%, the Ti content is (36-40) at.%, the contents of the Si, Y and N elements in the three sublayers are kept constant, the Si content is (1-3) at.%, the Y content is less than 0.1at.%, and the balance is N.
In the coating, the inner sublayer, the middle sublayer and the outer sublayer of the coating are formed by alternately depositing three modulation layers of TiSiN, TiAlN and YN, the thickness of each modulation layer is within 30nm, and the thicknesses of the inner sublayer, the middle sublayer and the outer sublayer are respectively (0.6-1.2) um.
Wherein, in the coating, the average grain size of the coating is within 30nm, and the total thickness of the coating is (1.8-3.6) um.
The invention provides a preparation method of the gradient structure TiAlSiYN multi-element nano coating, which comprises the following steps:
A. loading the cleaned substrate into a vacuum chamber of a coating device, vacuumizing and heating;
B. carrying out ion etching on the surface of the matrix;
C. depositing an inner layer with higher Al content by using a composite ion plating technology of cathodic arc plating and magnetron sputtering;
D. depositing the intermediate layer by using a composite ion plating technology of cathodic arc plating and magnetron sputtering;
E. and depositing the outer layer with low Al content by using a composite ion plating technology of cathodic arc plating and magnetron sputtering.
Wherein, in the step A, the step of vacuumizing and heating is to firstly vacuumize the back bottom to 5.8 multiplied by 10-2And when the temperature is lower than Pa, opening an auxiliary heating device of the furnace wall to heat the substrate, simultaneously opening a rotating power supply to enable the substrate to rotate ceaselessly, and heating for 50-80 min until the temperature of the substrate reaches 320-380 ℃.
In the step B of the method, argon is firstly introduced into the vacuum chamber, the flow of the argon is adjusted to ensure that the pressure is (1.0-2.5) multiplied by 10-1Pa, applying DC bias of (-100 to-200) V and pulse bias of (-200 to-400) V to the substrate, and using the ionized Ar+And etching the surface of the substrate for 30-80 min, wherein the temperature of the substrate is raised to 360-420 ℃.
Wherein,in the step C of the method, the inner layer with higher Al element content is deposited by sequentially closing the substrate bias voltage, closing argon gas and introducing nitrogen gas, adjusting the nitrogen gas flow to ensure that the working pressure is (1.9-2.6) Pa, and opening the high-alumina Ti100-xAlxAlloy target and Ti100-ySiyArc ion deposition of an alloy target, high-alumina Ti100-xAlxThe atomic content of the alloy target satisfies: x =60 to 67, Ti100-ySiyThe atomic content of the alloy target satisfies: y = 5-15, and high-aluminum Ti is adjusted100-xAlxAlloy target and Ti100-ySiyThe working power of each alloy target is (2-3) KW, the Y target is started to perform sputtering deposition at the same time, the sputtering power is (1-2) KW, bias voltage (-80-120) V is applied to the substrate, and deposition is performed for (20-40) min.
Wherein, in the step D of the method, the process of depositing the intermediate layer is to turn off the high-aluminum Ti100-xAlxAlloy target, open medium aluminum Ti100-xAlxAlloy target, medium Al Ti100-xAlxThe atomic content of the alloy target satisfies: x =50, medium aluminum Ti is adjusted100-xAlxThe working power of the alloy target is (2-3) KW and Ti100-ySiyAnd (3) keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and depositing for 20-40 min.
Wherein, in the step E of the method, the outer layer with lower Al element content is deposited by closing medium aluminum Ti100-xAlxAlloy target, open low-aluminum Ti100-xAlxAlloy target, low-Al Ti100-xAlxThe atomic content of the alloy target satisfies: x = 33-40, and low-aluminum Ti is adjusted100-xAlxThe working power of the alloy target is (2-3) KW and Ti100-ySiyAnd (4) continuously keeping the working power, the Y target sputtering power, the matrix bias voltage and the working pressure of the alloy target unchanged, and finishing the deposition after 20-40 min.
In the method, the coating equipment for preparing the gradient TiAlSiYN multi-element nano coating is multi-target plasma enhanced cathodic arc plating and magnetron sputtering composite ion plating filmThe system, wherein the deposition target comprises 4 pairs of arc targets and 1 pair of sputtering targets, and the 4 pairs of arc targets are respectively high-aluminum Ti100-xAlxAlloy target, medium aluminum Ti100-xAlxAlloy target, low-aluminum Ti100-xAlxAlloy target and Ti100-ySiyAlloy targets, 1 pair of sputtering targets was a Y target, and 5 pairs of targets were controlled individually.
Compared with the prior art, the invention has the following advantages:
1) the gradient-structure TiAlSiYN multi-element nano coating provided by the invention is composed of an inner layer, a middle layer and an outer layer which are changed in components, firstly, the gradient structure is favorable for relieving internal stress in the coating, so that the toughness of the coating is increased, meanwhile, each sublayer is formed by alternately depositing three modulation layers of TiSiN, TiAlN and YN, the crack expansion can be hindered by an interlayer interface in a multilayer structure, and the multilayer structure also breaks through a continuous columnar structure of the coating, so that the stress is released, and further the toughness of the coating is improved. The Y element in the coating can improve the high-temperature performance of the coating, and can purify grain boundaries or form YN with lower hardness, so that the toughness of the coating is further improved. In general, the TiAlSiYN multi-element nano coating with good toughness and hardness is obtained through the triple synergistic effect of the composition gradient structure, the interlayer interface and the rare earth Y element, so that the application range of the TiAlSiN coating is expanded.
2) The invention provides a preparation method of a gradient structure TiAlSiYN multi-element nano coating, which is a composite ion plating process mainly based on arc deposition and assisted by implanting trace elements through magnetron sputtering. The impurities adsorbed in the base material are released by heating before coating, and the ionized Ar + is adopted to carry out bombardment etching on the surface of the base body, so that the combination of the coating and the base body is enhanced, and the coating and the base body are combined well even if a transition layer process is not adopted. The cathodic arc plating technology ensures high deposition rate, can save the time of the coating process, can furthest inhibit the composition segregation phenomenon caused by using an excessively complicated electric arc alloy target by implanting trace elements through the magnetron sputtering technology, and ensures the stability of the coating composition and performanceMeanwhile, sputtering has certain interference effect on the electric arc deposition process, so that the vertical growth rate of the coating is reduced, the transverse diffusion of deposited atoms becomes more sufficient, and the densification of the coating is facilitated. When coating, three groups of Ti with different Al contents are added100-xAlxThe preparation of the gradient component coating is easy to realize by the independent control and switching of the target, the operation process is simple and is easy to master and control.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
Example 1
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.7 multiplied by 10 when the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device on the furnace wall is opened to heat the matrix, a rotating power supply is turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 345 ℃ after heating for 60 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 1.8 multiplied by 10-1Pa, then applying a DC bias of-200V and a pulsed bias of-350V to the substrate using ionized Ar+Etching the surface of the matrix for 40min, and raising the temperature of the matrix to 397 ℃; closing the substrate bias voltage, closing argon gas, introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.5Pa, and opening the high-aluminum Ti33Al67Alloy target and Ti85Si15The alloy target is subjected to arc ion deposition to adjust high-aluminum Ti33Al67Alloy target and Ti85Si15The working power of each alloy target is 2.2KW, the Y target is started to carry out sputtering deposition at the same time, the sputtering power is 1.2KW, bias voltage of-100V is applied to the substrate, and deposition is carried out for 30 min; shutting off high alumina Ti33Al67Alloy target, open medium aluminum Ti50Al50An alloy target is formed by a first alloy material,adjusting medium aluminum Ti50Al50The working power of the alloy target is 2.2KW and Ti85Si15Keeping the working power of the alloy target, the sputtering power of the Y target, the bias voltage of the substrate and the working pressure unchanged, and depositing for 30 min; closing medium aluminum Ti50Al50Alloy target, open low-aluminum Ti67Al33Alloy target, adjusted low-aluminum Ti67Al33The working power of the alloy target is 2.2KW and Ti85Si15And keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and finishing the deposition after 30 min.
Through detection, in the embodiment, the total thickness of the gradient-structure TiAlSiYN multi-element nano coating is 2.68um, the content of Al element in the innermost layer of the coating is 18.21at.%, the content of Ti element is 29.12at.%, the content of Si element is 1.88at.%, the content of Y element is 0.05at.%, and the content of N element is 50.74 at.%; the content of Al element in the intermediate layer was 13.82at.%, the content of Ti element was 34.48at.%, the content of Si element was 1.97at.%, the content of Y element was 0.05at.%, and the content of N element was 49.68 at.%; the outermost layer had an Al element content of 8.92at.%, a Ti element content of 38.88at.%, an Si element content of 1.92at.%, an Y element content of 0.06at.%, and an N element content of 50.22 at.%. The bonding strength of the coating and the substrate is 33N, the coating hardness is 28GPa, and the fracture toughness of the coating is 0.21 MPa.m1/2The friction coefficients of the coating at normal temperature and 400 ℃ are 0.63 and 0.65 respectively.
Example 2
Loading the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.0 × 10-2When Pa is needed, an auxiliary heating device on the furnace wall is opened to heat the matrix, a rotating power supply is simultaneously turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 325 ℃ after heating for 50 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 1.0 multiplied by 10-1Pa, then applying a DC bias of-100V and a pulsed bias of-200V to the substrate using ionized Ar+Para radicalEtching the surface of the substrate for 30min, and raising the temperature of the substrate to 368 ℃; closing the substrate bias voltage, closing argon gas and introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 1.9Pa, and opening the high-aluminum Ti35Al65Alloy target and Ti95Si5The alloy target is subjected to arc ion deposition to adjust high-aluminum Ti35Al65Alloy target and Ti95Si5The working power of each alloy target is 2KW, and the Y target is started to perform sputtering deposition at the same time, the sputtering power is 1KW, bias voltage of-80V is applied to the substrate, and deposition is performed for 20 min; shutting off high alumina Ti35Al65Alloy target, open medium aluminum Ti50Al50Alloy target, adjusted medium Al Ti50Al50The working power of the alloy target is 2KW and Ti95Si5Keeping the working power of the alloy target, the sputtering power of the Y target, the bias voltage of the substrate and the working pressure unchanged, and depositing for 20 min; closing medium aluminum Ti50Al50Alloy target, open low-aluminum Ti65Al35Alloy target, adjusted low-aluminum Ti65Al35The working power of the alloy target is 2KW and Ti95Si5And keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and finishing the deposition after 20 min.
Through detection, in the embodiment, the total thickness of the gradient-structure TiAlSiYN multi-element nano coating is 1.83um, the content of Al element in the innermost layer of the coating is 19.07at.%, the content of Ti element is 28.63at.%, the content of Si element is 1.21at.%, the content of Y element is 0.04at.%, and the content of N element is 51.05 at.%; the content of Al element in the intermediate layer was 14.67at.%, the content of Ti element was 32.59at.%, the content of Si element was 1.45at.%, the content of Y element was 0.04at.%, and the content of N element was 51.25 at.%; the outermost layer had an Al element content of 9.29at.%, a Ti element content of 37.03at.%, an Si element content of 1.42at.%, an Y element content of 0.04at.%, and an N element content of 52.22 at.%. The bonding strength of the coating and the substrate is 45N, the coating hardness is 26.7GPa, and the fracture toughness of the coating is 0.25 MPa-m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.65 and 0.69.
Example 3
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.5 multiplied by 10 after the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device on the furnace wall is opened to heat the matrix, a rotating power supply is turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 377 ℃ after heating for 80 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 2.5 multiplied by 10-1Pa, then applying a DC bias of-200V and a pulsed bias of-400V to the substrate using ionized Ar+Etching the surface of the matrix for 80min, and raising the temperature of the matrix to 415 ℃; closing the substrate bias voltage, closing argon gas and introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.6Pa, and opening the high-aluminum Ti40Al60Alloy target and Ti85Si15The alloy target is subjected to arc ion deposition to adjust high-aluminum Ti40Al60Alloy target and Ti85Si15The working power of each alloy target is 3KW, and the Y target is started to perform sputtering deposition at the same time, the sputtering power is 2KW, bias voltage of-80V is applied to the substrate, and deposition is performed for 40 min; shutting off high alumina Ti40Al60Alloy target, open medium aluminum Ti50Al50Alloy target, adjusted medium Al Ti50Al50The working power of the alloy target is 3KW and Ti85Si15Keeping the working power of the alloy target, the sputtering power of the Y target, the bias voltage of the substrate and the working pressure unchanged, and depositing for 40 min; closing medium aluminum Ti50Al50Alloy target, open low-aluminum Ti60Al40Alloy target, adjusted low-aluminum Ti60Al40The working power of the alloy target is 3KW and Ti85Si15And keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and finishing the deposition after 40 min.
Through detection, in the embodiment, the total thickness of the gradient-structured TiAlSiYN multi-element nano-coating is 3.47um, the content of Al element in the innermost layer of the coating is 15.86at.%, the content of Ti element is 31.53at.%, the content of Si element is 2.42at.%, and the content of Y element is 15.86at.%The amount was 0.07at.%, the N element content was 50.12 at.%; the content of Al element in the intermediate layer was 11.65at.%, the content of Ti element was 35.37at.%, the content of Si element was 2.61at.%, the content of Y element was 0.06at.%, and the content of N element was 50.31 at.%; the outermost layer had an Al element content of 7.39at.%, a Ti element content of 39.02at.%, an Si element content of 2.57at.%, an Y element content of 0.07at.%, and an N element content of 50.95 at.%. The bonding strength of the coating and the substrate is 32N, the coating hardness is 31.6GPa, and the fracture toughness of the coating is 0.19 MPa.m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.59 and 0.62.
Example 4
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.7 multiplied by 10 when the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device on the furnace wall is opened to heat the matrix, a rotating power supply is turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 366 ℃ after heating for 70 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 2.0 multiplied by 10-1Pa, then applying a DC bias of-150V and a pulsed bias of-300V to the substrate using ionized Ar+Etching the surface of the matrix for 60min, and raising the temperature of the matrix to 391 ℃; closing the substrate bias voltage, closing argon gas, introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.2Pa, and opening the high-aluminum Ti33Al67Alloy target and Ti90Si10Arc ion deposition of gold target to regulate high-alumina Ti33Al67Alloy target and Ti90Si10The working power of each alloy target is 2.5KW, and the Y target is started to perform sputtering deposition at the same time, the sputtering power is 2KW, a bias voltage of-90V is applied to the substrate, and the deposition is carried out for 40 min; shutting off high alumina Ti33Al67Alloy target, open medium aluminum Ti50Al50Alloy target, adjusted medium Al Ti50Al50The working power of the alloy target is 2KW and Ti90Si10The working power, Y target sputtering power, substrate bias voltage and working pressure of the alloy target are all ensuredKeeping unchanged, and depositing for 30 min; closing medium aluminum Ti50Al50Alloy target, open low-aluminum Ti67Al33Alloy target, adjusted low-aluminum Ti67Al33The working power of the alloy target is 3KW and Ti90Si10And continuously keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and depositing for 20 min.
Through detection, in the embodiment, the total thickness of the gradient-structure TiAlSiYN multi-element nano coating is 2.85um, the content of Al element in the innermost layer of the coating is 17.72at.%, the content of Ti element is 30.23at.%, the content of Si element is 2.01at.%, the content of Y element is 0.06at.%, and the content of N element is 49.98 at.%; the content of Al element in the intermediate layer was 14.33at.%, the content of Ti element was 32.63at.%, the content of Si element was 2.76at.%, the content of Y element was 0.05at.%, and the content of N element was 50.23 at.%; the outermost layer had an Al element content of 7.86at.%, a Ti element content of 39.14at.%, an Si element content of 1.29at.%, an Y element content of 0.06at.%, and an N element content of 56.65 at.%. The bonding strength of the coating and the substrate is 37N, the coating hardness is 27.8GPa, and the fracture toughness of the coating is 0.23 MPa.m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.61 and 0.65.
Comparative example 1
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.7 multiplied by 10 when the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device of the furnace wall is opened to heat the matrix, a rotating power supply is simultaneously turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 348 ℃ after heating for 60 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 1.8 multiplied by 10-1Pa, then applying a DC bias of-200V and a pulsed bias of-350V to the substrate using ionized Ar+Etching the surface of the matrix for 60min, and raising the temperature of the matrix to 401 ℃; closing the substrate bias voltage, closing argon gas and introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.5Pa, and opening the medium aluminum Ti50Al50Alloy target and Ti85Si15Alloy target, conditioningMedium aluminium Ti50Al50Alloy target and Ti85Si15The working power of the alloy target is 2.2KW respectively, bias voltage of-100V is applied to the substrate, and deposition is finished after 90 min.
Through detection, the total thickness of the gradient-structure TiAlSiN multi-element nano coating in the embodiment is 3.3um, the content of Al element in the coating is 13.68at.%, the content of Ti element is 26.73at.%, the content of Si element is 2.26at.%, and the content of N element is 57.33 at.%. The bonding strength of the coating and the substrate is 30N, the coating hardness is 34.3GPa, and the fracture toughness of the coating is 0.09 MPa.m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.79 and 0.76.
Comparative example 2
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.7 multiplied by 10 when the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device of the furnace wall is opened to heat the matrix, a rotating power supply is simultaneously turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 348 ℃ after heating for 60 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 1.8 multiplied by 10-1Pa, then applying a DC bias of-200V and a pulsed bias of-350V to the substrate using ionized Ar+Etching the surface of the matrix for 60min, and raising the temperature of the matrix to 401 ℃; closing the substrate bias voltage, closing argon gas and introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.5Pa, and opening the medium aluminum Ti50Al50Alloy target and Ti85Si15Alloy target, adjusted medium Al Ti50Al50Alloy target and Ti85Si15The working power of the alloy target is 2.2KW respectively, bias voltage of-100V is applied to the substrate, and deposition is finished after 90 min.
Through detection, the total thickness of the gradient-structure TiAlSiYN multi-element nano coating in the embodiment is 2.7um, the content of the Al element in the coating is 13.38at.%, the content of the Ti element is 25.48at.%, the content of the Si element is 2.58at.%, the content of the Y element is 0.05at.%, and the content of the N element is 58.51 at.%. The bonding strength of the coating and the substrate is 38N, and the coating is hardThe degree is 26.6GPa, and the fracture toughness of the coating is 0.12 MPa.m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.67 and 0.74.
Claims (10)
1. The gradient-structure TiAlSiYN multielement nano coating is characterized in that the coating is a quinary coating composed of five elements of Ti, Al, Si, Y and N, the coating structure is composed of an inner sublayer, a middle sublayer and an outer sublayer which are different in components, the Al content of each sublayer from the inner sublayer to the outer sublayer is sequentially reduced, the Ti content is sequentially increased, the Al content in the inner sublayer is (15-20) at.%, the Ti content is (28-32) at.%, the Al content in the middle sublayer is (10-15) at.%, the Ti content is (32-36) at.%, the Al content in the outer sublayer is (7-10) at.%, the Ti content is (36-40) at.%, the contents of the Si, Y and N elements in the three sublayers are kept constant, the Si content is (1-3) at.%, the Y content is less than 0.1at.%, and the balance is N.
2. The TiAlSiYN multielement nano-coating with the gradient structure as claimed in claim 1, wherein the three sublayers of the inner layer, the middle layer and the outer layer of the coating are formed by alternately depositing three modulation layers of TiSiN, TiAlN and YN, the thickness of the modulation layers is within 30nm, and the thicknesses of the three sublayers of the inner layer, the middle layer and the outer layer are respectively (0.6-1.2) um.
3. The gradient-structure TiAlSiYN multi-element nano coating is characterized in that the average grain size of the coating is within 30nm, and the total thickness of the coating is (1.8-3.6) um.
4. The preparation method of the gradient structure TiAlSiYN multi-component nano coating is characterized by comprising the following steps:
A. loading the cleaned substrate into a vacuum chamber of a coating device, vacuumizing and heating;
B. carrying out ion etching on the surface of the matrix;
C. depositing an inner layer with higher Al element content by using a composite ion plating technology of cathodic arc plating and magnetron sputtering;
D. depositing the intermediate layer by using a composite ion plating technology of cathodic arc plating and magnetron sputtering;
E. and depositing the outer layer with low Al element content by using a composite ion plating technology of cathodic arc plating and magnetron sputtering.
5. The method for preparing the gradient-structured TiAlSiYN multi-component nano-coating according to claim 4, wherein in the step A, the vacuum-pumping and heating are performed by firstly vacuumizing the back substrate to 5.8 x 10-2And when the temperature is lower than Pa, opening an auxiliary heating device of the furnace wall to heat the substrate, simultaneously opening a rotating power supply to enable the substrate to rotate ceaselessly, and heating for 50-80 min until the temperature of the substrate reaches 320-380 ℃.
6. The method for preparing the gradient-structure TiAlSiYN multi-element nano coating according to claim 4, wherein in the step B, the ion etching is performed by firstly introducing argon into a vacuum chamber, and adjusting the flow of the argon to ensure that the pressure is (1.0-2.5) x 10- 1Pa, applying DC bias of (-100 to-200) V and pulse bias of (-200 to-400) V to the substrate, and using the ionized Ar+And etching the surface of the substrate for 30-80 min, wherein the temperature of the substrate is raised to 360-420 ℃.
7. The method for preparing the gradient-structure TiAlSiYN multi-element nano coating according to claim 4, wherein the step C is carried out by sequentially closing the substrate bias, closing argon gas and introducing nitrogen gas, adjusting the nitrogen gas flow to ensure that the working pressure is (1.9-2.6) Pa and opening high-aluminum Ti100-xAlxAlloy target and Ti100-ySiyArc ion deposition of an alloy target, high-alumina Ti100-xAlxThe atomic content of the alloy target satisfies: x =60 to 67, Ti100-ySiyThe atomic content of the alloy target satisfies: y = 5-15, and high-aluminum Ti is adjusted100-xAlxAlloy target and Ti100-ySiyThe working power of each alloy target is (2-3) KW, the Y target is started to perform sputtering deposition at the same time, the sputtering power is (1-2) KW, bias voltage (-80-120) V is applied to the substrate, and deposition is performed for (20-40) min.
8. The method for preparing the gradient-structure TiAlSiYN multi-component nano-coating according to claim 4, wherein in the step D, the intermediate layer is deposited by shutting off high-aluminum Ti100-xAlxAlloy target, open medium aluminum Ti100-xAlxAlloy target, medium Al Ti100-xAlxThe atomic content of the alloy target satisfies: x =50, medium aluminum Ti is adjusted100-xAlxThe working power of the alloy target is (2-3) KW and Ti100-ySiyOperating Power of alloy target, YThe sputtering power of the target, the bias voltage of the substrate and the working pressure are kept unchanged, and deposition is carried out for 20-40 min.
9. The method for preparing the gradient-structure TiAlSiYN multi-element nano-coating according to claim 4, wherein in the step E, the outer layer with low Al content is deposited by closing medium Al Ti100-xAlxAlloy target, open low-aluminum Ti100-xAlxAlloy target, low-Al Ti100-xAlxThe atomic content of the alloy target satisfies: x = 33-40, and low-aluminum Ti is adjusted100-xAlxThe working power of the alloy target is (2-3) KW and Ti100-ySiyAnd (4) continuously keeping the working power, the Y target sputtering power, the matrix bias voltage and the working pressure of the alloy target unchanged, and finishing the deposition after 20-40 min.
10. The method for preparing the gradient-structure TiAlSiYN multi-component nano-coating according to any one of claims 4 to 9, wherein the coating equipment for preparing the gradient-structure TiAlSiYN multi-component nano-coating is a multi-target plasma enhanced cathodic arc plating and magnetron sputtering composite ion coating system, wherein the deposition targets used comprise 4 pairs of arc targets and 1 pair of sputtering targets, and the 4 pairs of arc targets are respectively high-alumina Ti100-xAlxAlloy target, medium aluminum Ti100-xAlxAlloy target, low-aluminum Ti100-xAlxAlloy target and Ti100-ySiyAlloy targets, 1 pair of sputtering targets was a Y target, and 5 pairs of targets were controlled individually.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910042017.6A CN109628896B (en) | 2019-01-17 | 2019-01-17 | Gradient structure TiAlSiYN multi-element nano coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910042017.6A CN109628896B (en) | 2019-01-17 | 2019-01-17 | Gradient structure TiAlSiYN multi-element nano coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109628896A true CN109628896A (en) | 2019-04-16 |
| CN109628896B CN109628896B (en) | 2020-10-30 |
Family
ID=66062062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910042017.6A Active CN109628896B (en) | 2019-01-17 | 2019-01-17 | Gradient structure TiAlSiYN multi-element nano coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109628896B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643952A (en) * | 2019-10-14 | 2020-01-03 | 四川大学 | Oxidation-resistant aluminum oxide/titanium nitride silicon composite coating and preparation method thereof |
| CN110643951A (en) * | 2019-10-14 | 2020-01-03 | 四川大学 | High-temperature oxidation resistant aluminum-chromium-silicon-nitrogen-aluminum oxide multilayer composite coating and preparation method thereof |
| CN110670019A (en) * | 2019-10-14 | 2020-01-10 | 四川大学 | Anti-crater wear aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating and preparation method thereof |
| CN114015981A (en) * | 2021-10-28 | 2022-02-08 | 中国科学院宁波材料技术与工程研究所 | Rare earth doped erosion-resistant protective coating and preparation method thereof |
| CN115074685A (en) * | 2022-06-27 | 2022-09-20 | 商丘市鸿大光电有限公司 | Preparation process of high-temperature-resistant TaVNb/TaVNbHfZr composite gradient barrier layer for purifying hydrogen catalyzed by tantalum/palladium |
| CN117904581A (en) * | 2024-03-15 | 2024-04-19 | 中南大学 | High-strength and high-toughness nano multilayer metal composite material and gradient interface design method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1867754A1 (en) * | 2006-05-26 | 2007-12-19 | Mitsubishi Materials Corporation | Cutting tool made of surface-coated cubic boron nitride-based ultra-high-pressure sintered material |
| CN103046001A (en) * | 2013-01-21 | 2013-04-17 | 浙江大学 | Amorphous carbon complex coating and preparation method thereof |
| CN104260440A (en) * | 2014-09-25 | 2015-01-07 | 温岭市温峤友德工具厂 | Nanocomposite coated tool containing Al, Ti, Si, Y and N and manufacturing method of nanocomposite coated tool |
| CN107858647A (en) * | 2017-11-09 | 2018-03-30 | 天津职业技术师范大学 | CrAlSiN nano-composite coatings that a kind of Al content changes in gradient and preparation method thereof |
-
2019
- 2019-01-17 CN CN201910042017.6A patent/CN109628896B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1867754A1 (en) * | 2006-05-26 | 2007-12-19 | Mitsubishi Materials Corporation | Cutting tool made of surface-coated cubic boron nitride-based ultra-high-pressure sintered material |
| CN103046001A (en) * | 2013-01-21 | 2013-04-17 | 浙江大学 | Amorphous carbon complex coating and preparation method thereof |
| CN104260440A (en) * | 2014-09-25 | 2015-01-07 | 温岭市温峤友德工具厂 | Nanocomposite coated tool containing Al, Ti, Si, Y and N and manufacturing method of nanocomposite coated tool |
| CN107858647A (en) * | 2017-11-09 | 2018-03-30 | 天津职业技术师范大学 | CrAlSiN nano-composite coatings that a kind of Al content changes in gradient and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ALEKSANDR V. PSHYK等: "Microstructure, phase omposition and mechanical properties of novel nanocomposite (TiAlSiY)N and nano-scale (TiAlSiY)N/MoN multifunctional heterostructures", 《SURFACE & COATINGS TECHNOLOGY》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643952A (en) * | 2019-10-14 | 2020-01-03 | 四川大学 | Oxidation-resistant aluminum oxide/titanium nitride silicon composite coating and preparation method thereof |
| CN110643951A (en) * | 2019-10-14 | 2020-01-03 | 四川大学 | High-temperature oxidation resistant aluminum-chromium-silicon-nitrogen-aluminum oxide multilayer composite coating and preparation method thereof |
| CN110670019A (en) * | 2019-10-14 | 2020-01-10 | 四川大学 | Anti-crater wear aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating and preparation method thereof |
| CN110643951B (en) * | 2019-10-14 | 2021-04-30 | 四川大学 | High-temperature oxidation resistant aluminum-chromium-silicon-nitrogen-aluminum oxide multilayer composite coating and preparation method thereof |
| CN114015981A (en) * | 2021-10-28 | 2022-02-08 | 中国科学院宁波材料技术与工程研究所 | Rare earth doped erosion-resistant protective coating and preparation method thereof |
| CN114015981B (en) * | 2021-10-28 | 2024-02-02 | 中国科学院宁波材料技术与工程研究所 | Rare earth doped erosion-resistant protective coating and preparation method thereof |
| CN115074685A (en) * | 2022-06-27 | 2022-09-20 | 商丘市鸿大光电有限公司 | Preparation process of high-temperature-resistant TaVNb/TaVNbHfZr composite gradient barrier layer for purifying hydrogen catalyzed by tantalum/palladium |
| CN115074685B (en) * | 2022-06-27 | 2023-10-27 | 商丘市鸿大光电有限公司 | Preparation process of high-temperature-resistant TaVNb/TaVNbHfZr composite gradient barrier layer for tantalum/palladium catalytic hydrogen purification |
| CN117904581A (en) * | 2024-03-15 | 2024-04-19 | 中南大学 | High-strength and high-toughness nano multilayer metal composite material and gradient interface design method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109628896B (en) | 2020-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109628896B (en) | Gradient structure TiAlSiYN multi-element nano coating and preparation method thereof | |
| Alami et al. | High power pulsed magnetron sputtering: Fundamentals and applications | |
| CN108642449B (en) | Superhard tough high-entropy alloy nitride nano composite coating hard alloy blade and preparation method thereof | |
| CN104928638A (en) | AlCrSiN-based multilayer nanometer composite cutter coating layer and preparation method thereof | |
| CN111349901B (en) | Preparation method of high-temperature-resistant alumina thick film coating for cutting tool | |
| CN108251797B (en) | TiAlN/CrN multilayer coating for titanium alloy cutting tool and preparation method thereof | |
| CN114717516B (en) | Strongly-combined high corrosion-resistant TiAl/Ti2Preparation method of AlC coating | |
| CN105862002A (en) | Oyster shell-like bionic multi-layer strengthened and toughened thin film | |
| CN111647851A (en) | Zr-B-N nano composite coating with high hardness and high toughness and preparation method thereof | |
| CN113174571B (en) | Ultra-microcrystalline titanium diboride composite coating and preparation method and application thereof | |
| CN111850484B (en) | Device and method for preparing tough amorphous carbon-based multiphase hybrid film | |
| CN103938157B (en) | A kind of ZrNbAlN superlattice coating and preparation method | |
| CN112080723A (en) | Nano multilayer composite anti-scratching film on surface of gold product and preparation method thereof | |
| CN106756841A (en) | A kind of preparation method of cutter composite coating | |
| CN110643953B (en) | Aluminum oxide/titanium aluminum nitrogen composite coating suitable for milling and preparation method thereof | |
| CN111304612B (en) | CrAlN/AlN nano multilayer coating with high hardness and high oxidation resistance and preparation method thereof | |
| CN110643936B (en) | Multilayer composite coating suitable for milling and preparation method thereof | |
| CN116445854A (en) | Superlattice tough high-entropy alloy nitride ceramic coating and preparation method thereof | |
| CN110656313B (en) | Zirconium aluminum nitride/aluminum oxide composite coating firmly combined with hard alloy and preparation method thereof | |
| CN110643951B (en) | High-temperature oxidation resistant aluminum-chromium-silicon-nitrogen-aluminum oxide multilayer composite coating and preparation method thereof | |
| CN110670019B (en) | Anti-crater wear aluminum-titanium-zirconium-nitrogen and aluminum oxide multilayer composite coating and preparation method thereof | |
| CN111489956B (en) | AlCrNbSiTi high-entropy alloy oxide insulating film material for transistor and preparation method thereof | |
| CN114807849A (en) | Nano composite high-entropy nitride coating and composite deposition method thereof | |
| CN108149198A (en) | A kind of WC hard alloy film and its gradient layer technology room temperature preparation method | |
| CN110670020B (en) | Zirconium-aluminum-nitrogen-aluminum oxide multilayer composite coating firmly combined with metal ceramic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |