CN115125595B - Preparation method of titanium-manganese alloy coating - Google Patents
Preparation method of titanium-manganese alloy coating Download PDFInfo
- Publication number
- CN115125595B CN115125595B CN202210719117.XA CN202210719117A CN115125595B CN 115125595 B CN115125595 B CN 115125595B CN 202210719117 A CN202210719117 A CN 202210719117A CN 115125595 B CN115125595 B CN 115125595B
- Authority
- CN
- China
- Prior art keywords
- titanium
- manganese alloy
- alloy coating
- manganese
- metal
- 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.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 121
- 239000011248 coating agent Substances 0.000 title claims abstract description 120
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910000914 Mn alloy Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000010936 titanium Substances 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000011572 manganese Substances 0.000 claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000005530 etching Methods 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005238 degreasing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 71
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 25
- 238000000137 annealing Methods 0.000 abstract description 17
- 238000007747 plating Methods 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract 1
- 239000007962 solid dispersion Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 18
- 239000000956 alloy Substances 0.000 description 11
- 238000009713 electroplating Methods 0.000 description 10
- 238000005121 nitriding Methods 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005255 carburizing Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
- C23C8/68—Boronising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrochemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
The invention discloses a preparation method of a titanium-manganese alloy coating, which comprises the following steps: (1) Plating a layer of metal Mn on the metal Ti sheet with the surface subjected to etching treatment; (2) And (3) carrying out high-temperature annealing treatment on the titanium sheet with the metal Mn coating on the surface to obtain the titanium-manganese coating material. The titanium-manganese alloy coating provided by the invention adopts vacuum, ar and N 2 Or NH 3 The Mn is respectively permeated to the surface of the metal titanium in a solid dispersion way under the action of high temperature by atmosphere annealing treatment, so that the combination of titanium and manganese is very tight, and the prepared titanium-manganese coating has very high strength and has better adhesive force with a substrate; the whole preparation process is in an oxygen isolation state, and the prepared titanium-manganese alloy coating has high purity. The titanium-manganese alloy coating prepared by the process is compact and smooth, high in strength, strong in coating adhesion and low in cost, and meanwhileThe preparation process is simple, and is easy to implement in process and mass production.
Description
Technical Field
The invention belongs to the field of alloy materials, relates to a preparation method of an alloy coating material, and in particular relates to a preparation method of a titanium-manganese alloy coating material.
Background
With the development of scientific technology, many new material surface technologies such as electroplating, electroless plating, overlaying, thermal spraying, chemical conversion coating, vapor deposition, casting infiltration and the like are continuously emerging, and the technologies have better effects on improving the strength and the service life of the material. In recent years, the standards for hydrogen storage capability and EMD preparation are continuously improved, and more titanium alloy materials are widely used in the standards, wherein the titanium manganese alloy materials are the most representative. The titanium-manganese alloy has the advantages of large hydrogen storage capacity, easy activation, capability of absorbing and releasing hydrogen at low pressure, abundant raw materials, low cost, easy alloy processing and the like. Thus, titanium manganese alloy as AB 2 Typical representatives of the type of hydrogen storage alloys are widely studied.
In addition, in the process of preparing the EMD, the titanium-manganese alloy has special properties, such as high strength, strong corrosion resistance and good conductivity, and is also widely applied. In addition, the ratio of titanium to manganese can be regulated according to the use requirement of the application environment, so that the chemical components, tissues and performances of the titanium-manganese alloy layer can be optimally matched, and the difficulty of poor casting performance of the titanium alloy material can be overcome. At present, the preparation of the titanium-manganese alloy coating material mainly adopts the processes of infiltration casting, mixed slurry preparation, sintering and the like to form the titanium-based titanium-manganese alloy coating material.
Patent CN 87216402 discloses a composite anode for electrolysis, mainly the method for preparing anode material for titanium-based titanium-manganese coating: the method comprises the steps of coating a mixed slurry on the surface of a pure titanium matrix by adopting a brushing or spraying method, and then sintering to prepare a composite coating anode with a coating firmly and metallurgically bonded with the matrix, wherein the brushing or spraying process is complex, the artificial influence factors are large, the coating is extremely easy to be uneven, colloid is adopted as a binder, and products are easy to be polluted due to incomplete glue discharge or cracking; in addition, when the slurry containing the manganese powder and the titanium powder is prepared for brushing, the titanium powder and the manganese powder are oxidized, so that the oxygen content of the coating material is too high, the purity and the crystallinity of the titanium-manganese alloy coating material are reduced, and the service life of the titanium-manganese alloy coating material is influenced.
Patent CN 101603180a discloses a preparation method of a titanium-manganese alloy coating: in a vacuum furnace, heating manganese powder or manganese blocks loaded in a molybdenum boat by adopting pulse current to obtain manganese vapor, so that the manganese vapor is adsorbed on the surface of a titanium plate and is diffused into the titanium plate to form a Mn-doped layer. Although the titanium-manganese alloy coating prepared by the method has uniform surface, the preparation process is complex and has high requirements on a preparation device; although the method can reduce the pollution of oxygen atoms, when gas phase manganese permeation is adopted, the diffusion mode of gas at high temperature is complex, which can lead to poor adhesive force of the prepared titanium-manganese coating material and reduce the strength of the coating material.
Therefore, there is a need to develop a preparation method of a titanium-manganese alloy coating with tight titanium-manganese combination, high strength, low cost, low impurity content, high crystallinity and simple process.
Disclosure of Invention
The invention aims to provide a preparation method of a titanium-manganese alloy coating, which adopts processes such as electrodeposition, magnetron sputtering, chemical vapor deposition, atomic layer deposition and the like to plate a layer of compact metal Mn film on the surface of a metal Ti sheet, and the Ti sheet with the metal Mn film is placed in a high-temperature furnace for high-temperature annealing treatment, so that metal manganese is uniformly diffused on the surface of the metal titanium, and a titanium-manganese alloy coating material with very tight combination of titanium and manganese is prepared. The method has the advantages of simple process, low cost, short time, low impurity content of the coating material, no pollution in the whole process and easy mass production.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the titanium-manganese alloy coating comprises the following steps:
step 1: sequentially degreasing and polishing the surface of the metal Ti sheet, then etching the surface by acid to increase the roughness of the surface and improve the adhesive force of the metal Mn plating layer, and plating a layer of dense metal Mn film on the surface of the metal Ti sheet by adopting processes such as electrodeposition, magnetron sputtering, chemical vapor deposition, atomic layer deposition and the like, wherein the preparation process is further preferably electrochemical deposition.
Step 2: placing Ti sheet with metal Mn film plated on surface in tubular furnace for high temperature annealing treatment in vacuum and N atmosphere 2 、Ar 2 、NH 3 One of them.
And 3, doping (N, C, S, B) the titanium-manganese alloy coating material to improve the internal crystallization strength of the titanium-manganese alloy coating material and enhance the intermetallic acting force so as to be suitable for more environments.
Preferably, the acid used in step 1 is one or more of oxalic acid, nitric acid and citric acid.
Preferably, the thickness of the metal Mn plating layer prepared by the electrodeposition process in step 1 is 5-25 μm.
Preferably, in step 2, the vacuum level required in the preparation of the titanium manganese coating is 4X 10 -3 ～1×10 -2 Pa, using N 2 、Ar 2 、NH 3 When the pressure is normal pressure.
Preferably, in the step 2, the temperature required in the process of preparing the titanium-manganese coating is 1000-1400 ℃, the annealing time is 0.5-2 h, and the annealing temperature is 1200 ℃ and the annealing time is 2h.
Preferably, in the step 2, the coating thickness of the prepared titanium-manganese alloy coating material is 10-20 mu m, wherein the Mn content is 40-60%.
Preferably, in the step 3, the nitrogen source used for doping the titanium-manganese alloy coating is N 2 、NH 4 Cl、NH 3 One or more of them further select NH 3 As a nitrogen source.
Preferably, in the step 3, the carbon source used for doping the titanium-manganese alloy coating is one or more of methane and ethane, and methane is further selected as the carbon source.
Preferably, in the step 3, the sulfur source used for doping the titanium-manganese alloy coating is one or more of sublimed sulfur, settled sulfur and refined sulfur.
Preferably, in the step 3, the boron source used for doping the titanium-manganese alloy coating is KBF 4 、Fe 2 B, one or two of the following.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the metal Mn plating layer is prepared on the surface of the metal Ti sheet by adopting an electrodeposition process, and a brushing or spraying slurry method is not adopted, so that the prepared titanium-manganese alloy coating is not polluted by an organic solvent, the coating purity is higher, the surface of the coating is compact and flat, and the problem of oxygen atom pollution caused by oxidation of manganese powder when the slurry is used can be avoided.
(2) The invention adopts the high-vacuum solid-phase manganese-permeation process to prepare the titanium-manganese alloy coating, the preparation process is simpler, and compared with the gas-phase manganese-permeation process of pulse current, the invention can save the cost of equipment.
(3) The titanium-manganese alloy coating material is in a high vacuum environment in the process of preparing the titanium-manganese alloy coating, has extremely low oxygen content, further avoids the oxidization problem in the process of preparing the titanium-manganese alloy coating material, and has better purity and crystallinity.
(4) The invention adopts the solid phase infiltration of the metal manganese and the metal titanium to prepare the titanium-manganese alloy coating, the combination between the metal manganese and the titanium is firm, the coating strength is high, and the coating has better mechanical property.
(5) The preparation method has the advantages of simple preparation process, strong operability, short time and low energy consumption, and is easy to implement industrially and realize mass production.
Drawings
Fig. 1 is an SEM image of the titanium-manganese alloy coating obtained in examples 1, 2, and 3, wherein (a) is example 1, (b) is example 2, and (c) is example 3.
Fig. 2 shows XRD patterns of the titanium-manganese alloy coatings obtained in examples 1, 2 and 3, wherein (a) is example 1, (b) is example 2, and (c) is example 3.
Detailed Description
The present invention will be described in further detail with reference to examples, but is not limited to the scope of the invention.
Example 1:
sequentially degreasing and polishing the surface of the metal titanium sheet, and then carrying out surface etching treatment on the polished metal titanium sheet by using 10% hydrofluoric acid (or 4% nitric acid and 12% citric acid). Electroplating a layer of metal manganese on the surface of a metal titanium sheet by adopting an electrochemical deposition process, wherein the electroplating process comprises the following parameters: mn (Mn) 2+ 15g/L，(NH 4 ) 2 SO 4 80g/L, current density 300mA/cm 2 The temperature is 40 ℃ and the electroplating time is 1h, so that the obtained metal manganese coating is 10 mu m. Placing titanium sheet with metal manganese coating in vacuum furnace, and vacuum degree in preparation process is maintained at 4×10 -3 ～1×10 -2 Pa, the annealing temperature is 1100 ℃, the annealing time is 0.5h, and finally the titanium-manganese coating material is obtained.
The scanning electron microscope diagram is shown in fig. 1 (a), and the phase analysis is shown in fig. 2 (a). As can be seen from a scanning electron microscope image and an XRD phase, the prepared titanium-manganese alloy coating material has a relatively flat surface and slightly agglomerated phenomenon, and the phase is mainly Mn 2 Ti, and not detecting the phases of oxides of titanium and manganese, shows that the titanium-manganese alloy material prepared by the process has higher purity and does not contain any impurity. Meanwhile, the mechanical property test is carried out on the titanium-manganese coating material, the Vickers hardness of the titanium-manganese coating material is 390HV, the tensile strength of the coating material is 324Mpa, and the elongation is 28.74%.
Example 2:
sequentially degreasing and polishing the surface of the metal titanium sheet, and then carrying out surface etching treatment on the polished metal titanium sheet by using 10% hydrofluoric acid (or 4% nitric acid and 12% citric acid). Electroplating a layer of metal manganese on the surface of a metal titanium sheet by adopting an electrochemical deposition process, wherein the electroplating process comprises the following parameters: mn (Mn) 2+ 15g/L，(NH 4 ) 2 SO 4 80g/L, current density 300mA/cm 2 The temperature is 40 ℃ and the electroplating time is 1h, so that the obtained metal manganese coating is 10 mu m. Placing titanium sheet with metal manganese coating in vacuum furnace, and vacuum degree in preparation process is maintained at 4×10 -3 Pa～1×10 -2 Pa, annealing temperature of 1100 ℃, annealing timeAnd (3) obtaining the titanium-manganese coating material after 2 hours.
The scanning electron microscope diagram is shown in fig. 1 (b), and the phase analysis is shown in fig. 2 (b). As can be seen from a scanning electron microscope image and an XRD phase, the surface evenness of the prepared titanium-manganese alloy coating material is further improved along with the extension of the annealing time, the agglomeration phenomenon is gradually reduced, and the phase is still Mn 2 Ti, the phase of the oxide of titanium and manganese is not detected at the same time, compared with the annealing for 0.5h in the embodiment 1, the prepared titanium-manganese alloy material has higher peak strength and narrower half-width, which shows that the crystallinity of the titanium-manganese alloy material is enhanced when the annealing time is prolonged, and the strength of the material is improved. The titanium-manganese coating material is subjected to mechanical property test, the Vickers hardness of the titanium-manganese coating material is 442HV, the tensile strength of the coating material is 351Mpa, and the elongation is 23.15%.
Example 3:
sequentially degreasing and polishing the surface of the metal titanium sheet, and then carrying out surface etching treatment on the polished metal titanium sheet by using 10% hydrofluoric acid (or 4% nitric acid and 12% citric acid). Electroplating a layer of metal manganese on the surface of a metal titanium sheet by adopting an electrochemical deposition process, wherein the electroplating process comprises the following parameters: mn (Mn) 2+ 15g/L，(NH 4 ) 2 SO 4 80g/L, current density 300mA/cm 2 The temperature is 40 ℃ and the electroplating time is 1h, so that the obtained metal manganese coating is 10 mu m. Placing titanium sheet with metal manganese coating in vacuum furnace, and vacuum degree in preparation process is maintained at 4×10 -3 ～1×10 -2 Pa, the annealing temperature is 1200 ℃, the annealing time is 2 hours, and finally the titanium-manganese coating material is obtained.
The scanning electron microscope diagram is shown in fig. 1 (c), and the phase analysis is shown in fig. 2 (c). As can be seen from a scanning electron microscope image and an XRD phase, compared with the example 2, the annealing temperature is increased to 1200 ℃, and the surface of the prepared titanium-manganese alloy coating material is compact and smooth, and no agglomeration phenomenon occurs. Still Mn in phase 2 Ti, in which the phases of oxides of titanium and manganese are not detected at the same time, the titanium-manganese alloy materials prepared in example 1 and example 2 have higher peak intensities, narrower half-widths, and further improved crystallinity and strength.
The titanium-manganese coating material is subjected to mechanical property test, the Vickers hardness of the titanium-manganese coating material is 489HV, the tensile strength of the coating material is 421Mpa, the elongation is 17.35%, and the coating material and the substrate are strongly combined.
Example 4:
other conditions are the same as those of example 3, a titanium-manganese alloy coating material is prepared, N permeation treatment is carried out by gas phase nitriding, and a nitrogen source adopts NH 3 The nitriding time is 3h, the nitriding temperature is 850 ℃, the nitrogen-doped titanium-manganese alloy coating material is prepared, the mechanical property test is carried out on the coating material, the Vickers hardness of the coating material is 526HV, the tensile strength of the coating material is 478Mpa, and the elongation is 14.39%.
Example 5:
other conditions were the same as in example 3, a titanium-based titanium-manganese alloy coating material was prepared, which was subjected to N-permeation treatment by gas phase nitriding, nitrogen source was nitrogen gas, nitriding time was 3 hours, nitriding temperature was 850 ℃, a nitrogen-doped titanium-manganese alloy coating material was prepared, and was subjected to mechanical property test, which had a Vickers hardness of 498HV, a tensile strength of 436Mpa, and an elongation of 16.27%. Compared with ammonia gas as nitrogen source, the mechanical property of the titanium-manganese alloy coating is improved less, mainly due to NH 3 The N-H bond energy is lower, and compared with N (identical to that in nitrogen), N in nitrogen is easy to decompose, so that nitrogen atoms are easy to enter into crystal lattices of the titanium-manganese alloy, and the strength of the titanium-manganese alloy coating material is improved.
Example 6:
other conditions were the same as in example 3, a titanium-manganese alloy coating material was prepared, which was subjected to C-cementation by a gas phase carburization method, a methane gas was used as a carbon source, the carburization time was 6 hours, the nitriding temperature was 900 ℃, a carbon-doped titanium-manganese alloy coating material was prepared, and was subjected to a mechanical property test, which had a Vickers hardness of 534HV, a tensile strength of 483MPa, and an elongation of 13.15%.
Example 7:
other conditions were the same as in example 3, a titanium-manganese alloy coating material was prepared, which was subjected to C-permeation treatment by a gas phase carburizing method, an ethane gas was used as a carbon source, a carburizing time was 6 hours, a carburizing temperature was 900 ℃, a carbon-doped titanium-manganese alloy coating material was prepared, and was subjected to a mechanical property test, which had a vickers hardness of 529HV, a tensile strength of 471Mpa, and an elongation of 14.12%. Compared with ethane gas as a carbon source, the mechanical property of the titanium-manganese alloy coating is improved less, mainly because methane is easier to crack compared with hydrocarbon bonds of ethane, in addition, carbon in the ethane exists in a C-C bond form, the bond energy is higher, and the carbon atom is not easy to deviate from.
Example 8:
other conditions were the same as in example 3, a titanium-manganese alloy coating material was prepared, the coating material was subjected to S-permeation treatment by a solid-phase embedding method, a sulfur source was subjected to sublimation sulfur, the sulfur permeation time was 4 hours, the sulfur permeation temperature was 750 ℃, a sulfur-doped titanium-manganese alloy coating material was prepared, and the coating material was subjected to mechanical property test, the Vickers hardness was 516HV, the tensile strength of the coating material was 475Mpa, and the elongation was 13.43%.
Example 9:
other conditions were the same as in example 3, a titanium-manganese alloy coating material was prepared, S-permeation treatment was performed by a solid-phase embedding method, a sulfur source was precipitated sulfur, the sulfur permeation time was 4 hours, the sulfur permeation temperature was 750 ℃, a sulfur-doped titanium-manganese alloy coating material was prepared, and a mechanical property test was performed on the titanium-manganese alloy coating material, the Vickers hardness was 518HV, the tensile strength of the coating material was 479Mpa, and the elongation was 13.41%
Example 10:
other conditions were the same as in example 3, a titanium-based titanium-manganese alloy coating material was prepared, the coating material was subjected to S permeation treatment by a solid-phase embedding method, a sulfur source was subjected to refined sulfur permeation for 4 hours at a temperature of 750 ℃ to prepare a sulfur-doped titanium-manganese alloy coating material, and the coating material was subjected to mechanical property test, and had a Vickers hardness of 514HV, a tensile strength of 470Mpa and an elongation of 13.42%.
Example 11:
other conditions are the same as those of example 3, a titanium-manganese alloy coating material is prepared, B infiltration treatment is carried out by adopting a solid-phase embedding method, and a boron source adopts KBF 4 Preparing boron-doped titanium-manganese alloy coating material with a sulfurizing time of 4h and a sulfurizing temperature of 950 ℃, and carrying out mechanical property test on the coating material, wherein the Vickers hardness of the coating material is 526HVThe tensile strength of the material is 475Mpa, and the elongation is 15.43%.
Example 12:
other conditions are the same as those of example 3, a titanium-manganese alloy coating material is prepared, B infiltration treatment is carried out by adopting a solid-phase embedding method, and a boron source adopts Fe 2 B, the sulfurizing time is 4 hours, the sulfurizing temperature is 950 ℃, the boron-doped titanium-manganese alloy coating material is prepared, the mechanical property test is carried out on the boron-doped titanium-manganese alloy coating material, the Vickers hardness of the boron-doped titanium-manganese alloy coating material is 519HV, the tensile strength of the coating material is 473Mpa, and the elongation is 15.64%.
Claims (8)
1. The preparation method of the titanium-manganese alloy coating is characterized by comprising the following steps of:
step 1: pretreatment is carried out on the Ti surface;
step 2: preparing a metal Mn film on the pretreated Ti surface by an electrochemical deposition method;
step 3: carrying out high-temperature heat treatment on the titanium sheet with the metal Mn film plated on the surface in a certain atmosphere to enable the metal Mn and Ti to mutually infiltrate and form a titanium-manganese alloy coating;
wherein the heat treatment atmosphere in the step 3 is vacuum or N 2 、Ar、NH 3 One of the following; when a vacuum atmosphere is adopted, the vacuum degree is 4 multiplied by 10 -3 ~1×10 -2 Pa, using N 2 、Ar、NH 3 When the pressure is normal pressure, the atmosphere is N 2 、Ar、NH 3 Wherein one gas atmosphere or a mixed atmosphere of at least one gas; the heat treatment temperature in the step 3 is 1000-1400 ℃, and the heat treatment time is 0.5-2 h.
2. The method for preparing the titanium-manganese alloy coating according to claim 1, which is characterized in that: and step 1, sequentially degreasing, polishing and then etching the surface of the metal Ti sheet by using acid, wherein the etching agent adopted in the etching process is one or more of hydrofluoric acid, oxalic acid, nitric acid and citric acid.
3. The method for preparing the titanium-manganese alloy coating according to claim 1 or 2, characterized in that: in the step 2, the thickness of the metal Mn film is 5-25 μm.
4. The method for preparing the titanium-manganese alloy coating according to claim 1, which is characterized in that: and carrying out doping modification treatment on the prepared titanium-manganese alloy coating, wherein the doping element is at least one of N, C, S, B.
5. The method for preparing the titanium-manganese alloy coating according to claim 4, which is characterized in that: when the doping element is N, the nitrogen source is N 2 、NH 4 Cl、NH 3 At least one of them.
6. The method for preparing the titanium-manganese alloy coating according to claim 4, which is characterized in that: when the doping element is C, the carbon source is one or two of methane and ethane.
7. The method for preparing the titanium-manganese alloy coating according to claim 4, which is characterized in that: when the doping element is S, the sulfur source is one or more of sublimated sulfur, settled sulfur and refined sulfur.
8. The method for preparing the titanium-manganese alloy coating according to claim 4, which is characterized in that: when the doping element is B, the boron source is KBF 4 、Fe 2 B, one or two of the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210719117.XA CN115125595B (en) | 2022-06-23 | 2022-06-23 | Preparation method of titanium-manganese alloy coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210719117.XA CN115125595B (en) | 2022-06-23 | 2022-06-23 | Preparation method of titanium-manganese alloy coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115125595A CN115125595A (en) | 2022-09-30 |
| CN115125595B true CN115125595B (en) | 2023-11-24 |
Family
ID=83379166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210719117.XA Active CN115125595B (en) | 2022-06-23 | 2022-06-23 | Preparation method of titanium-manganese alloy coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115125595B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902535A (en) * | 1987-12-31 | 1990-02-20 | Air Products And Chemicals, Inc. | Method for depositing hard coatings on titanium or titanium alloys |
| CN101603180A (en) * | 2009-06-09 | 2009-12-16 | 湖南泰阳新材料有限公司 | A kind of electrolytic manganese dioxide production preparation method of coating titanium anode |
| CN108315783A (en) * | 2018-02-09 | 2018-07-24 | 中南大学 | In the method that flexible metal manganese is electroplated in aluminium surface |
| CN109267114A (en) * | 2018-10-22 | 2019-01-25 | 中国科学院金属研究所 | A kind of preparation method of cobalt-manganese spinel coating |
| CN109504987A (en) * | 2018-12-20 | 2019-03-22 | 中南大学 | A kind of titanium-based composite anode for electrolytic manganese and preparation method thereof, application |
| CN109504912A (en) * | 2018-12-22 | 2019-03-22 | 中南大学 | A kind of high corrosion resisting stainless steel of cupric titanium cobalt and its process and heat treatment method |
| CN109837570A (en) * | 2017-11-27 | 2019-06-04 | 李娜 | A kind of environment-friendly high-efficiency titanium manganese alloy pre-treatment electroplating technology |
| CN113388798A (en) * | 2021-05-14 | 2021-09-14 | 王念贵 | Corrosion-resistant aluminum alloy coating material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005106067A2 (en) * | 2004-04-23 | 2005-11-10 | Molecular Fx | Thin-film coating for wheel rims |
-
2022
- 2022-06-23 CN CN202210719117.XA patent/CN115125595B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902535A (en) * | 1987-12-31 | 1990-02-20 | Air Products And Chemicals, Inc. | Method for depositing hard coatings on titanium or titanium alloys |
| CN101603180A (en) * | 2009-06-09 | 2009-12-16 | 湖南泰阳新材料有限公司 | A kind of electrolytic manganese dioxide production preparation method of coating titanium anode |
| CN109837570A (en) * | 2017-11-27 | 2019-06-04 | 李娜 | A kind of environment-friendly high-efficiency titanium manganese alloy pre-treatment electroplating technology |
| CN108315783A (en) * | 2018-02-09 | 2018-07-24 | 中南大学 | In the method that flexible metal manganese is electroplated in aluminium surface |
| CN109267114A (en) * | 2018-10-22 | 2019-01-25 | 中国科学院金属研究所 | A kind of preparation method of cobalt-manganese spinel coating |
| CN109504987A (en) * | 2018-12-20 | 2019-03-22 | 中南大学 | A kind of titanium-based composite anode for electrolytic manganese and preparation method thereof, application |
| CN109504912A (en) * | 2018-12-22 | 2019-03-22 | 中南大学 | A kind of high corrosion resisting stainless steel of cupric titanium cobalt and its process and heat treatment method |
| CN113388798A (en) * | 2021-05-14 | 2021-09-14 | 王念贵 | Corrosion-resistant aluminum alloy coating material |
Non-Patent Citations (3)
| Title |
|---|
| "Catalytic effects of NH4+ on hydrogen evolution and manganese electrodeposition on stainless steel";Yang, Fan 等;《TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA》;第29卷(第11期);第2430-2439页 * |
| "Synthesis of self-organized mixed oxide nanotubes by sonoelectrochemical anodization of Ti-8Mn alloy";Mohapatra, Susanta K.等;《ELECTROCHIMICA ACTA》;第53卷(第2期);第590-597页 * |
| "钛－锰合金涂层电极在下田锰矿的应用";韦运县;《中国锰业》;第5页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115125595A (en) | 2022-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112609165A (en) | Composite coating on surface of bipolar plate of stainless steel-based fuel cell and preparation method thereof | |
| KR20150105742A (en) | Preparing method of alloy catalyst using poly dopamine coating and alloy catalyst thereby | |
| CN101265603A (en) | Multiple layer hydrogen infiltration -resistant compound film preparation method | |
| CN108149183B (en) | Hard alloy with surface hardness in gradient distribution and preparation method thereof | |
| CN109306445B (en) | Preparation method of Ti-Al-C series MAX phase coating on surface of titanium or titanium alloy | |
| EP4088332A1 (en) | Carbon coated hydrogen fuel cell bipolar plates | |
| WO2014104717A1 (en) | Steel sheet coated with aluminum-magnesium, and method for manufacturing same | |
| WO2023197469A1 (en) | High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexisting coating, and preparation method therefor and use thereof | |
| CN113088836A (en) | Method for preparing carbon fiber reinforced aluminum matrix composite material by electric arc spraying | |
| CN115125595B (en) | Preparation method of titanium-manganese alloy coating | |
| CN109267114B (en) | Preparation method of cobalt-manganese spinel coating | |
| CN106715743B (en) | Solid oxide fuel cell steel and its manufacturing method | |
| JP3081765B2 (en) | Carbon member and method of manufacturing the same | |
| TWI376833B (en) | Method for preparing a surface modification coating of metal bipolar plates | |
| CN114737229B (en) | Method for preparing platinum modified aluminide coating on surface of monocrystal superalloy | |
| CN114231892B (en) | Modification method of metallic titanium surface | |
| CN115161607A (en) | Rare earth doped high-entropy alloy nitride coating and preparation method thereof | |
| JP2002020882A (en) | Sliding member and its production method | |
| CN113042343A (en) | Preparation method of super-hydrophobic intermetallic compound-based protective layer with high mechanical stability and corrosion resistance | |
| US20100323101A1 (en) | Method for preparing surface modification coating of metal bipolar plates | |
| CN111041428A (en) | Method for preparing nano carbide based on EB-PVD (electron beam-physical vapor deposition) to enhance stability of matrix | |
| CN114231894B (en) | Low-temperature high-efficiency ion nitrogen aluminum co-permeation surface modification method | |
| CN111705318A (en) | Five-element titanium alloy getter based on foam metal substrate | |
| CN110644028A (en) | Method for rapidly preparing expansion alpha phase on surface of metal material | |
| CN114686804B (en) | Composite coating of oxide dispersion reinforced steel 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 |