CN113981392A - Ti-Al-C MAX phase coating and low-temperature phase forming preparation method thereof - Google Patents
Ti-Al-C MAX phase coating and low-temperature phase forming preparation method thereof Download PDFInfo
- Publication number
- CN113981392A CN113981392A CN202111175820.0A CN202111175820A CN113981392A CN 113981392 A CN113981392 A CN 113981392A CN 202111175820 A CN202111175820 A CN 202111175820A CN 113981392 A CN113981392 A CN 113981392A
- Authority
- CN
- China
- Prior art keywords
- coating
- alc
- max phase
- temperature
- low
- 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.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 26
- 238000004544 sputter deposition Methods 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 16
- 229910004349 Ti-Al Inorganic materials 0.000 claims abstract description 13
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 13
- 229910004692 Ti—Al Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000012495 reaction gas Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 238000005477 sputtering target Methods 0.000 claims abstract description 3
- 239000013077 target material Substances 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 230000007704 transition Effects 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 12
- 229910010038 TiAl Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000000151 deposition Methods 0.000 description 20
- 230000008021 deposition Effects 0.000 description 20
- 238000000168 high power impulse magnetron sputter deposition Methods 0.000 description 20
- 239000010936 titanium Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 6
- 229910001069 Ti alloy Inorganic materials 0.000 description 6
- 238000005137 deposition process Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000012876 topography Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- -1 argon ion Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C14/0635—Carbides
-
- 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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a Ti3AlC2The low-temperature phase formation preparation method of the MAX phase coating is characterized by comprising the steps of taking a Ti-Al composite target as a sputtering target material, taking hydrocarbon gas as a reaction gas source, adopting a high-power pulse magnetron sputtering technology, sputtering the surface of the substrate by a short pulse of 100-x-a C coating; heat treating said TiAlxCoating with-C to obtain Ti3AlC2MAX phase coating, and the heat treatment temperature is 600-700 ℃. The method can prepare Ti at lower temperature3AlC2MAX phase coating. The invention also provides the Ti-Al-C MAX phase coating prepared by the method.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to Ti3AlC2A low temperature phase forming preparation method of MAX phase coating.
Background
The MAX phase material is a large class of thermodynamically stable layered high-performance ceramic metal material with a close-packed hexagonal structure and a general formula of Mn+1AXnWhere the M site is a transition metal element including Ti, Cr, etc., the a site is usually a third or fourth main group element of the periodic table, such as Al, Si, etc., and the X site is C or N, it is understood that the metal carbide or metal nitride nano-layered compound is divided by a single layer of a atoms. In general, M-X is bound by strong covalent and ionic bonds, while M-A is bound by means of relatively weak metallic bonds. The unique layered structure and bonding mode enable the MAX phase to have the excellent performances of metal and ceramic, such as excellent mechanical stability, high hardness, good thermal shock resistance, strong corrosion resistance and high-temperature oxidation resistance, good electrical conductivity and thermal conductivity, self-healing property and processability.
In the general formula Mn+1AXnIn the MAX phase crystal structure, the value of n is n +1, the value of the n is mainly 1, 2 and 3, and the MAX phase is divided into 211, 312 and 413 phases according to the difference of the n values. Typical Al-containing MAX phase materials are formed by forming protective Al2O3The layer shows remarkable high-temperature oxidation resistance and corrosion resistance, and the most representative Ti-Al-C system and Cr-Al-C system are formed by mixing Ti-Al-C compound and Al2O3The thermal expansion coefficient of the alloy is close to that of the alloy, and the alloy becomes a proper protective coating for the base bodies of stainless steel, titanium alloy, nickel-based high-temperature alloy and the like.
However, the MAX phase material needs a longer diffusion coefficient to distribute elements in the synthesis process due to a longer c-axis and a complex crystal structure, so that the synthesis preparation of the MAX phase is strongly dependent on the temperature, and the lower temperature cannot meet the synthesis conditions, and particularly, the performance of the higher-order 312 phase and 413 phase is improved and a higher synthesis temperature is also needed compared with that of the 211 phase.Ti in Ti-Al-C system3AlC2The common block preparation methods, such as a hot pressing method, a plasma sintering method and the like, have the synthesis temperature of over 1200 ℃, but the synthesis temperature of a coating film system can be reduced due to the short diffusion length, but the synthesis temperature is in the range of 800-1000 ℃ in the magnetron sputtering and cathodic arc plating in PVD which is the main technology for preparing MAX phase coatings at present.
The high preparation temperature of the MAX phase limits the application of the MAX phase on a temperature sensitive substrate, and how to reduce the preparation temperature of the MAX phase, especially the synthesis of the higher-order 312 phase, can expand the application range thereof, and is also one of the bottlenecks of the MAX phase material at present.
Disclosure of Invention
The invention provides a low-temperature phase-forming preparation method of a Ti-Al-C MAX phase coating, which can prepare Ti at a lower temperature3AlC2MAX phase coating.
Ti3AlC2A method for the low temperature, phase forming preparation of a MAX phase coating comprising:
(1) taking Ti-Al composite target as sputtering target material, hydrocarbon gas as reaction gas source, adopting high power pulse magnetron sputtering technology, sputtering the surface of the substrate with the frequency of 500-1000Hz, the duty ratio of 5-10 percent and the short pulse of 100-200 mu s to obtain TiAlx-a C coating;
(2) heat treating said TiAlxCoating with-C to obtain Ti3AlC2MAX phase coating, and the heat treatment temperature is 600-700 ℃.
The invention enables the HiPIMS to provide enough energy to TiAl by regulating and controlling the parameters of the high-power impulse magnetron sputtering (HiPIMS) technologyxTi-C crystal lattice is formed in the-C coating, and then TiAl is enabled to be subjected to a lower heat treatment temperature of 600-700 DEG CxDiffusion of Al ions in the-C coating into the Ti-C lattice to form Ti3AlC2MAX phase coating, thereby enabling Ti to be obtained at lower temperatures3AlC2MAX phase coating, as compared with the prior art, needs more than 900 ℃ to form complete Ti3AlC2The heat treatment temperature of the coating is lower compared with that of the coating with the MAX phase of 312 phase and 413 phase。
In the step (1):
the Ti-Al element ratio of the Ti-Al composite target is 2: 1.2-1.5.
The flow rate of the hydrocarbon gas is 5-10 sccm. Further, the hydrocarbon gas is methane or acetylene.
Sputtering the surface of the counter substrate to obtain TiAlxBefore the C coating, the substrate is subjected to a plasma glow etching treatment. So that the surface of the substrate is cleaner.
Further, the plasma is any one of argon and nitrogen.
Further, the plasma glow etching parameters are as follows: the plasma flow is 30-35 sccm, the ion source voltage is 1000-1200V, the substrate is biased to-250-150V, and the etching time is 20-40 min.
After the plasma glow etching treatment is carried out on the substrate, the reaction source is closed, the Ti-Al composite target is started, and a transition layer is sputtered on the surface of the substrate.
Further, the transition layer is a TiAl compound.
The sputtering parameters are as follows: the sputtering power is 1800-2400W, and the substrate bias is-100-0V.
Before sputtering a transition layer on the surface of the substrate, introducing protective gas, wherein the flow rate of the protective gas is 150-250 sccm, and the air pressure of the cavity is 0.6-1.2 Pa.
To avoid substrate layers from bonding with TiAlxInterdiffusion of elements in the-C coating to give the final Ti3AlC2The presence of other nanocrystalline particles in the MAX phase coating affects Ti3AlC2Purity of the MAX phase coating and addition of a transition layer enables the coefficient of thermal expansion between the coating and the substrate to be over-matched to cause TiAlxThe binding force of the-C coating is increased.
In the step (2), the heat treatment time is 60-180 min.
The Ti-Al-C MAX phase coating is prepared by the low-temperature phase-forming preparation method of the Ti-Al-C MAX phase coating, and the thickness of the Ti-Al-C MAX phase coating is 2-4 μm.
Compared with the prior art, the invention has the advantages that:
(1) the high-power pulse magnetron sputtering HiPIMS power supply is used for carrying out pulse sputtering on the Ti-Al composite target, the duty ratio is low, the peak power density of the target is high, the ionization rate of target elements and reaction gas is improved, the plasma energy in the sputtering process is improved, and Ti can be prepared at a low heat treatment temperature subsequently3AlC2312 is MAX phase, thereby reducing the preparation of Ti by the traditional magnetron sputtering or cathodic arc plating in the prior PVD technology3AlC2312 is the required phase forming temperature of MAX phase (900-1200 ℃ in the conventional method), the invention generates relatively pure Ti at 600-700 ℃3AlC2312 is MAX phase, which provides a reliable idea for the preparation of MAX phase coating.
(2) The high-power pulse HiPIMS power sputtering deposition technology integrates the advantages of low-temperature deposition, smooth surface, no particle defect, high ionization rate of cathodic arc ion plating metal, strong film bonding force and compact coating of the traditional magnetron sputtering, and simultaneously improves the problem of target poisoning arcing, so that the prepared coating has no particle accumulation phenomenon on the surface, the particles are more refined, the surface is more compact, flat and smooth, and the roughness is as low as 15-19 nm.
Drawings
FIG. 1 is the discharge characteristic of a HiPIMS power supply for medium-high power pulse magnetron sputtering in the preparation of the coating of the invention.
FIG. 2 is an XRD spectrum of Ti-Al-C MAX phase coating prepared by the present invention in example 1 and comparative example 1 in a deposition state and an annealing state.
FIG. 3 is a surface topography of a Ti-Al-C MAX phase coating produced in example 1 of the present invention.
FIG. 4 is a surface topography of a Ti-Al-C MAX phase coating made according to comparative example 1 of the present invention.
FIG. 5 is an XRD spectrum of Ti-Al-C MAX phase coating prepared by the present invention in example 2 and comparative example 2 in as-deposited and as-annealed states.
FIG. 6 is a surface topography of a Ti-Al-C MAX phase coating produced in example 2 of the present invention.
FIG. 7 is a surface topography of a Ti-Al-C MAX phase coating made according to comparative example 2 of the present invention.
Detailed Description
Example 1:
in this example, the substrate material was 1Cr11Ni2W2MoV stainless steel, and Ti on the surface of the substrate3AlC2The specific preparation steps of the MAX phase coating are as follows:
step 1: sequentially grinding the surface of 1Cr11Ni2W2MoV stainless steel by using 400# to 2000# SiC sand paper, and polishing for 20min by using diamond grinding paste;
step 2: and (3) placing the polished 1Cr11Ni2W2MoV stainless steel substrate in acetone for ultrasonic cleaning for 10min, drying by cold air, and adhering the dried substrate on a sample rack by using conductive adhesive for later use.
And step 3: placing the sample rack with the substrate in the deposition chamber, and vacuumizing to 3 × 10 with a mechanical pump and a molecular pump-5And (3) setting the temperature of the cavity to be 100 ℃ below Pa, introducing 34sccm of high-purity argon into the vacuum cavity, setting the current of a linear anode ion source to be 0.2A and the bias voltage of the substrate to be-200V, and etching and cleaning the surface of the 1Cr11Ni2W2MoV stainless steel substrate for 30 min.
And 4, step 4: the deposition conditions of the Ti-Al transition layer are the same as those in the following step 5, the difference is that the introduced gas is different, the hydrocarbon reaction gas is not introduced into the deposition of the transition layer, the high-purity argon gas of 200sccm is introduced into the deposition of the transition layer,
and 5: TiAl is obtained by deposition by adopting high-power pulse HiPIMS technologyxAnd (3) coating C, introducing high-purity argon of 200sccm, introducing high-purity methane reaction gas of 7.5sccm, sputtering a composite target with a ratio of Ti to Al of 2:1.5, setting a sputtering source HiPIMS power supply to be 500Hz, a period of 2000 mus, a duty ratio of 5%, a pulse time of 100 mus, setting the power to be constant in the deposition process to be 2000W, and setting the discharge characteristics in the deposition process as shown in figure 1, wherein the substrate bias voltage is 0V, the cavity pressure is 1Pa, and the deposition time is 120 min.
Step 6: the obtained deposition TiAlxThe C coating is placed in an annealing furnace with a vacuum degree of less than 2X 10-3Pa, keeping the temperature at 700 ℃ for 90min to obtain Ti3AlC2MAX phase.
Comparative example 1:
this example is a comparative example to example 1 above.
In this example, the substrate was the same as in example 1, and the pretreatment and surface argon ion glow etching of the substrate were the same, except that in the steps (4) and (5), the Ti-Al transition layer and TiAl were formedxThe deposition of the-C coating is carried out by using a traditional direct current magnetron sputtering technology instead of HiPIMS high-power pulse magnetron sputtering, and a direct current sputtering source is also set to be constant power of 2000W during the deposition process. The subsequent heat treatment conditions were also the same as in example 1.
FIG. 2 shows the as-deposited and as-annealed X-ray diffraction patterns of the coatings obtained in example 1 and comparative example 1. As can be seen from FIG. 2, the composition of the as-deposited coating obtained by HiPIMS high-power pulse magnetron sputtering is TiAlxThe compound and the deposited coating obtained by the direct current magnetron sputtering in the comparative example are amorphous, and then Ti is obtained by the HiPIMS high-power pulse magnetron sputtering technology in the heat treatment process of 700 ℃ at the same annealing temperature3AlC2312 is MAX phase, and only Ti is generated under the DC magnetron sputtering technology of the comparative example2AlC 211 is a MAX phase. The XRD spectrum also has peaks partly derived from the matrix and transition layers.
Fig. 3 and 4 are surface topography diagrams of the coatings prepared in the above example 1 and the comparative example 1, respectively, and the coating prepared by HiPIMS high power pulse magnetron sputtering has a more compact and flat surface and finer particles than the coating prepared by dc magnetron sputtering.
Example 2:
in this example, the base material was TC4 titanium alloy, and Ti on the surface of the base was3AlC2The specific preparation steps of the MAX phase coating are as follows:
step 1: sequentially grinding the surface of TC4 titanium alloy by using 400# to 2000# SiC sand paper, and then polishing for 20min by using diamond grinding paste;
step 2: and (3) placing the polished TC4 titanium alloy matrix in acetone for ultrasonic cleaning for 10min, and then drying by cold air and adhering the titanium alloy matrix on a sample rack by using conductive adhesive for later use.
And step 3: placing the sample rack with the substrate in the deposition chamber, and vacuumizing to 3 × 10 with a mechanical pump and a molecular pump-5And (3) setting the temperature of the cavity to be 100 ℃ below Pa, introducing 34sccm of high-purity argon into the vacuum cavity, setting the current of the linear anode ion source to be 0.2A and the bias voltage of the matrix to be-200V, and etching and cleaning the surface of the TC4 titanium alloy matrix for 30 min.
And 4, step 4: the deposition conditions of the Ti-Al transition layer are the same as those in the following step 5, the difference is that the introduced gas is different, the hydrocarbon reaction gas is not introduced into the deposition of the transition layer, only the high-purity argon gas of 200sccm is introduced,
and 5: TiAl is obtained by deposition by adopting high-power pulse HiPIMS technologyxAnd (3) coating C, introducing high-purity argon of 200sccm, introducing high-purity methane reaction gas of 7.5sccm, sputtering a composite target with a ratio of Ti to Al of 2:1.5, setting a sputtering source HiPIMS power supply to be 500Hz, a period of 2000 mus, a duty ratio of 5%, a pulse time of 100 mus, setting the power to be constant in the deposition process to be 2000W, and setting the discharge characteristics in the deposition process as shown in figure 1, wherein the substrate bias voltage is 0V, the cavity pressure is 1Pa, and the deposition time is 120 min.
Step 6: the obtained deposition TiAlxThe C coating is placed in an annealing furnace with a vacuum degree of less than 2X 10-3Pa, keeping the temperature at 700 ℃ for 90min to obtain Ti3AlC2MAX phase.
Comparative example 2:
this example is a comparative example to example 2 above.
In this example, the substrate was the same as that of example 2, and the pretreatment and surface argon ion glow etching of the substrate were the same, except that in the steps (4) and (5), the Ti — Al transition layer and TiAl were formedxThe deposition of the-C coating is carried out by using a traditional direct current magnetron sputtering technology instead of HiPIMS high-power pulse magnetron sputtering, and a direct current sputtering source is also set to be constant power of 2000W during the deposition process. The subsequent heat treatment conditions were also the same as in example 2.
FIG. 5 shows the as-deposited and as-annealed X-ray diffraction patterns of the coatings obtained in example 2 and comparative example 2. From the figure5, the deposition state of the coating obtained by the HiPIMS high-power pulse magnetron sputtering is different from that of the coating obtained under the direct current magnetron sputtering (DC) and is amorphous, and the component of the deposition state coating obtained by the HiPIMS high-power pulse magnetron sputtering is TiAl compoundxIn the subsequent annealing treatment, only the HiPIMS high-power pulse magnetron sputtering technology obtains Ti in the heat treatment process at 700 DEG C3AlC2312 is MAX phase, and only Ti is generated under the DC magnetron sputtering technology of the comparative example2AlC 211 is a MAX phase. The XRD spectrum also has peaks partly derived from the matrix and transition layers.
Fig. 6 and 7 are surface topography diagrams of the coatings prepared in the above example 2 and comparative example 2, respectively, the coatings prepared by dc magnetron sputtering have hillock features composed of aggregated spherical particles, while the coatings prepared by HiPIMS high power pulse magnetron sputtering have significantly improved coalescence, refined particles on the coating surface, denser coating, and smoother surface.
The present inventors also conducted experiments under other base materials and conditions listed in the present specification with reference to the manner of example 1 and example 2, and obtained the same results.
In conclusion, Ti can be reduced by the HiPIMS high-power pulse magnetron sputtering technology3AlC2312 is the phase temperature of the MAX phase and the quality of the coating produced is better.
The above embodiments are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the above embodiments.
Claims (10)
1. Ti3AlC2A method for the low temperature, phase forming preparation of a MAX phase coating, comprising:
(1) taking Ti-Al composite target as sputtering target material, hydrocarbon gas as reaction gas source, adopting high power pulse magnetron sputtering technology, sputtering the surface of the substrate with the frequency of 500-1000Hz, the duty ratio of 5-10 percent and the short pulse of 100-200 mu s to obtain TiAlx-a C coating;
(2) heat treating said TiAlxCoating with-C to obtain Ti3AlC2MAX phase coating, and the heat treatment temperature is 600-700 ℃.
2. The Ti of claim 13AlC2The low-temperature phase forming preparation method of the MAX phase coating is characterized in that the Ti-Al element ratio of the Ti-Al composite target is 2: 1.2-1.5.
3. The Ti of claim 13AlC2The low-temperature phase forming preparation method of the MAX phase coating is characterized in that the flow of the hydrocarbon gas is 5-10 sccm.
4. The Ti of claim 13AlC2The low-temperature phase forming preparation method of the MAX phase coating is characterized in that TiAl is obtained by sputtering the surface of the substratexBefore the C coating, the substrate is subjected to a plasma glow etching treatment.
5. The Ti of claim 43AlC2A method for the low temperature, phase forming preparation of MAX phase coatings, characterised in that the plasma is argon or nitrogen.
6. The Ti of claim 43AlC2The low-temperature phase forming preparation method of the MAX phase coating is characterized in that the plasma glow etching parameters are as follows: the plasma flow is 30-35 sccm, the ion source voltage is 1000-1200V, the substrate is biased to-250-150V, and the etching time is 20-40 min.
7. The Ti of claim 43AlC2The low-temperature phase forming preparation method of the MAX phase coating is characterized in that after the substrate is subjected to plasma glow etching treatment, the reaction gas source is closed, the Ti-Al composite target is started, and a transition layer is sputtered on the surface of the substrate.
8. Root of herbaceous plantThe Ti of claim 73AlC2The low-temperature phase forming preparation method of the MAX phase coating is characterized in that the transition layer is a TiAl inter-compound.
9. The Ti of claim 73AlC2The low-temperature phase forming preparation method of the MAX phase coating is characterized in that the sputtering parameters are as follows: the sputtering power is 1800-2400W, and the substrate bias is-100-0V.
10. The Ti according to any of claims 1-93AlC2The Ti-Al-C MAX phase coating prepared by the low-temperature phase-forming preparation method of the MAX phase coating is characterized in that the thickness of the Ti-Al-C MAX phase coating is 2-4 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111175820.0A CN113981392A (en) | 2021-10-09 | 2021-10-09 | Ti-Al-C MAX phase coating and low-temperature phase forming preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111175820.0A CN113981392A (en) | 2021-10-09 | 2021-10-09 | Ti-Al-C MAX phase coating and low-temperature phase forming preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113981392A true CN113981392A (en) | 2022-01-28 |
Family
ID=79737907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111175820.0A Pending CN113981392A (en) | 2021-10-09 | 2021-10-09 | Ti-Al-C MAX phase coating and low-temperature phase forming preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113981392A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115369367A (en) * | 2022-07-08 | 2022-11-22 | 中国科学院宁波材料技术与工程研究所 | Conductive hydrophilic MAX phase coating on surface of medical cutter as well as preparation method and application thereof |
| CN116219381A (en) * | 2022-12-13 | 2023-06-06 | 中国科学院宁波材料技术与工程研究所 | Low-temperature preparation method and application of MAX phase coating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108330452A (en) * | 2018-01-12 | 2018-07-27 | 中国科学院宁波材料技术与工程研究所 | The preparation method of MAX phase coatings |
| CN109642305A (en) * | 2016-08-31 | 2019-04-16 | 菲特尔莫古布尔沙伊德有限公司 | Sliding members containing MAX phase coating |
| CN113235062A (en) * | 2021-07-12 | 2021-08-10 | 中国科学院宁波材料技术与工程研究所 | MAX-phase multilayer composite coating and preparation method and application thereof |
| CN113249683A (en) * | 2021-07-11 | 2021-08-13 | 中国科学院宁波材料技术与工程研究所 | MAX phase solid solution composite coating with high conductivity, corrosion resistance and long service life, and preparation method and application thereof |
-
2021
- 2021-10-09 CN CN202111175820.0A patent/CN113981392A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109642305A (en) * | 2016-08-31 | 2019-04-16 | 菲特尔莫古布尔沙伊德有限公司 | Sliding members containing MAX phase coating |
| CN108330452A (en) * | 2018-01-12 | 2018-07-27 | 中国科学院宁波材料技术与工程研究所 | The preparation method of MAX phase coatings |
| CN113249683A (en) * | 2021-07-11 | 2021-08-13 | 中国科学院宁波材料技术与工程研究所 | MAX phase solid solution composite coating with high conductivity, corrosion resistance and long service life, and preparation method and application thereof |
| CN113235062A (en) * | 2021-07-12 | 2021-08-10 | 中国科学院宁波材料技术与工程研究所 | MAX-phase multilayer composite coating and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115369367A (en) * | 2022-07-08 | 2022-11-22 | 中国科学院宁波材料技术与工程研究所 | Conductive hydrophilic MAX phase coating on surface of medical cutter as well as preparation method and application thereof |
| CN115369367B (en) * | 2022-07-08 | 2023-11-10 | 中国科学院宁波材料技术与工程研究所 | Conductive hydrophilic MAX phase coating on surface of medical cutter and preparation method and application thereof |
| CN116219381A (en) * | 2022-12-13 | 2023-06-06 | 中国科学院宁波材料技术与工程研究所 | Low-temperature preparation method and application of MAX phase coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109161841B (en) | AlCrN/AlCrSiN superhard nano composite multilayer coating and preparation method and application thereof | |
| CN113981392A (en) | Ti-Al-C MAX phase coating and low-temperature phase forming preparation method thereof | |
| CN111349901B (en) | Preparation method of high-temperature-resistant alumina thick film coating for cutting tool | |
| CN108796453B (en) | High-temperature wear-resistant AlCrSiN nano composite coating and preparation method thereof | |
| CN109735804B (en) | Metal carbon compound coating and preparation method thereof | |
| CN111155064A (en) | Method for preparing TiAlSiN composite coating by high-power pulse magnetron sputtering | |
| CN115386828B (en) | MAX phase solid solution coating, preparation method and application thereof | |
| CN111455333B (en) | Al-Cr-O film with Al-rich corundum structure and preparation method thereof | |
| CN108330452A (en) | The preparation method of MAX phase coatings | |
| CN108330455B (en) | Cr (chromium)2Preparation method of coating with adjustable AlC phase purity | |
| KR20110065038A (en) | Manufacturing method for palladium-copper-nickel alloy hydrogen separation membrane | |
| CN110257771A (en) | A kind of c-CrAlSiN hard coat of high Al content and preparation method thereof | |
| CN112853281B (en) | Carbon-based multilayer film and preparation method and application thereof | |
| CN111304612B (en) | CrAlN/AlN nano multilayer coating with high hardness and high oxidation resistance and preparation method thereof | |
| Tsai et al. | Structural, electro-optical, and mechanical properties of reactively sputtered (TiZrHf) N coatings | |
| CN116219381A (en) | Low-temperature preparation method and application of MAX phase coating | |
| CN105970170B (en) | The method of hafnium/silicon nitride conduction and anti-corrosion multilayered structure coating is prepared on magnesium alloy | |
| CN108130518A (en) | A kind of AlB with high high-temp stability2Type WB2(N) ganoine thin film and preparation method thereof | |
| CN112553580B (en) | Diboride composite coating and preparation method and application thereof | |
| CN112391593B (en) | CrB with high Cr content and good toughness 2 -Cr coating and preparation process thereof | |
| CN114807849A (en) | Nano composite high-entropy nitride coating and composite deposition method thereof | |
| CN114672777A (en) | Antioxidant Cr/CrAl nano multilayer coating and preparation method thereof | |
| CN114086122A (en) | Ceramic-based gradient plating layer based on high film-substrate binding force on copper substrate and preparation method thereof | |
| CN109023278B (en) | Method for preparing high-strength copper-aluminum alloy | |
| CN113913746A (en) | Coating, method for producing the same and device |
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 |