CN111206241A - Method for improving high-temperature oxidation resistance of titanium-based alloy through hydrothermal treatment - Google Patents
Method for improving high-temperature oxidation resistance of titanium-based alloy through hydrothermal treatment Download PDFInfo
- Publication number
- CN111206241A CN111206241A CN201911108371.0A CN201911108371A CN111206241A CN 111206241 A CN111206241 A CN 111206241A CN 201911108371 A CN201911108371 A CN 201911108371A CN 111206241 A CN111206241 A CN 111206241A
- Authority
- CN
- China
- Prior art keywords
- titanium
- based alloy
- hydrothermal treatment
- oxidation resistance
- temperature oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 109
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 107
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 85
- 239000010936 titanium Substances 0.000 title claims abstract description 85
- 230000003647 oxidation Effects 0.000 title claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 45
- 238000010335 hydrothermal treatment Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 30
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- -1 halogen salt Chemical class 0.000 claims abstract description 18
- 150000002367 halogens Chemical class 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 150000002221 fluorine Chemical class 0.000 claims description 3
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 18
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 16
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 14
- 229910010038 TiAl Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000007547 defect Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 230000004584 weight gain Effects 0.000 description 10
- 235000019786 weight gain Nutrition 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 235000013024 sodium fluoride Nutrition 0.000 description 8
- 239000011775 sodium fluoride Substances 0.000 description 8
- 229910004349 Ti-Al Inorganic materials 0.000 description 7
- 229910004692 Ti—Al Inorganic materials 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 235000003270 potassium fluoride Nutrition 0.000 description 7
- 239000011698 potassium fluoride Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000000861 blow drying Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007676 flexural strength test Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to the field of alloy material surface treatment, in particular to a method for improving high-temperature oxidation resistance of a titanium-based alloy through hydrothermal treatment. The method comprises the following steps: preparing a salt solution by using halogen salt containing halogen elements, placing the titanium-based alloy in the salt solution, placing the titanium-based alloy in a sealed reactor for at least one time of hydrothermal treatment, and finally cooling, cleaning and drying. The method can effectively improve the high-temperature oxidation resistance of the titanium-based alloy; the problem of reduction of mechanical property of the titanium-based alloy can be avoided; the treatment method is simple and efficient, has lower operation difficulty, lower cost, lower equipment requirement and higher treatment efficiency, and is more suitable for industrial production.
Description
Technical Field
The invention relates to the field of alloy material surface treatment, in particular to a method for improving high-temperature oxidation resistance of a titanium-based alloy through hydrothermal treatment.
Background
The TiAl-based intermetallic compound alloy (referred to as TiAl alloy for short) has the characteristics of low density (50 percent of that of the existing widely used Ni-based alloy), high specific strength and specific rigidity, good high-temperature creep property and the like. Can be widely applied to high-temperature components of automobile or aircraft engines, such as: the TiAl-based alloy is an ideal material for replacing a nickel-based high-temperature alloy, and is considered to be one of novel light high-temperature structural materials with application prospects. However, when the TiAl alloy is used at temperatures exceeding 750 ℃, the high temperature oxidation resistance of the TiAl alloy deteriorates rapidly, since at higher temperatures the affinity of titanium and aluminum for oxygen is very highFormed on the surface of the alloy is TiO2And Al2O3The mixed layer has a high growth rate of the oxide film, and is likely to be exfoliated. This seriously affects the usability of the alloy.
In order to overcome the defects, scholars at home and abroad adopt methods such as alloying, ion implantation, surface coating, anodic oxidation and the like to modify so as to improve the service temperature of the titanium-aluminum alloy. The alloy design mainly comprises two aspects, namely, the content of basic element Al in the TiAl alloy is increased, which is really beneficial to improving the oxidation resistance of the TiAl alloy, but the content of Al is not too high, otherwise, the brittle TiAl is precipitated once3Will affect its mechanical properties. Secondly, by adding a third or a plurality of alloy elements, such as: nb, Sb, Si, Cr, Y, Mo and the like can also effectively improve the high-temperature oxidation resistance of the TiAl alloy, but the mechanical property of the TiAl alloy is generally reduced due to the excessively high addition amount. Although the ion implantation method has controllable implantation amount and good repeatability, the related equipment is expensive and has low production efficiency, and the change depth of the TiAl alloy composition is only limited to the range with a shallow surface (<1 μm). Protective coatings, e.g. metal coatings MCrAl (Y), ceramic coatings (e.g. SiO)2、Al2O3And ZrO2Etc.) and diffusion coatings (e.g., Al, Si, etc.) each have certain problems, although they act as barriers to oxygen penetration into the substrate. The interdiffusion between the metal coating and the substrate is serious, a hard and brittle phase is easily separated out from an interface, and simultaneously, Kenkard holes are generated, so that the bonding strength of the coating and the substrate is seriously reduced; the diffusion coating has a large difference in thermal expansion coefficient from the substrate.
The Chinese patent office discloses an invention patent application of a method for improving high-temperature oxidation resistance of a titanium-based alloy on 2018, 9 and 4, with the application publication number of CN108486631A, and improves the high-temperature oxidation resistance of the titanium-based alloy by preparing a layer of oxide film doped with active elements on the surface of titanium base. The technical scheme can effectively improve the high-temperature oxidation resistance of the titanium-based alloy, but the adoption of the electrodeposition mode has certain pollution and certain limitation in the large-scale industrial production process, and the doping of the rare earth element also improves the treatment cost.
Disclosure of Invention
The invention provides a method for improving the high-temperature oxidation resistance of titanium-based alloy by hydrothermal treatment, aiming at solving the problems that the existing titanium-based alloy has insufficient high-temperature oxidation resistance, the mechanical property of the titanium-based alloy is reduced, the existing optimization method has high cost and certain pollution, or the existing treatment mode has larger limitation and is mostly only suitable for flat alloy treatment. The invention aims to: firstly, the high-temperature oxidation resistance of the titanium-based alloy is improved; simplifying the treatment method, reducing the treatment operation difficulty, and being simpler and more efficient; thirdly, the cost is reduced, the treatment efficiency is improved, the method is easy to realize and is more suitable for industrial production; fourthly, the problems of reducing the mechanical property of the titanium-based alloy and the like are not generated.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method for improving high-temperature oxidation resistance of titanium-based alloy by hydrothermal treatment,
the method comprises the following steps:
preparing a salt solution by using halogen salt containing halogen elements, placing the titanium-based alloy in the salt solution, placing the titanium-based alloy in a sealed reactor for at least one time of hydrothermal treatment, and finally cooling, cleaning and drying.
The method is simple and efficient, and the method comprises the steps of firstly carrying out pretreatment operations including descaling, deoiling and the like on the carrier (titanium-based alloy), then placing the pretreated carrier in the prepared salt solution, and doping the halogen element in a high-pressure high-temperature environment of hydrothermal reaction. Compared with the doping modification of metal elements, the doping of the halogen elements is difficult to form defects after doping because atoms of the halogen elements are smaller, and the doping of the metal elements is easy to generate defects due to the volume effect and the doping difficulty is larger because the atoms of the metal elements are generally larger in volume after doping. In addition, the doping of the halogen element and the doping of the metal element are different in doping mode, the doping position of the halogen element is located at the original defect position of the titanium-based alloy, which is equivalent to filling the defect of the titanium-based alloy, the defect can be reduced by the filling mode, the doping of the metal element is carried out by replacing the metal element in the titanium-based alloy, the defect is reduced by the doped metal element atom extrusion mode after replacement, and the defect can be reduced by the replacement and extrusion mode. Compared with a filling doping mode, the defects are reduced through replacement and extrusion, new defects are easily generated, the original crystal structure is damaged, the mechanical property of the titanium-based alloy is easily reduced, the problem does not exist in halogen element doping, the halogen element doping through hydrothermal treatment is more efficient and uniform, the controllability is higher, the crystal structure cannot be damaged, the operation equivalent to repairing is carried out on the original defects, and therefore the mechanical property of the titanium-based alloy is prevented from being reduced while the high-temperature oxidation resistance of the titanium-based alloy is improved. In addition, the hydrothermal treatment can be carried out for multiple times, because the halogen element can be filled and diffused to the deeper layer of the titanium-based alloy in the hydrothermal treatment process, the limit performance of high-temperature oxidation resistance generated after multiple times of hydrothermal treatment cannot be obviously improved, but the performance of the high-temperature oxidation resistance is more excellent in a long-time high-temperature environment.
Compared with the doping of metal elements, the fluorination also has the advantages that fluorine is more difficult to oxidize, and the existing form after doping is more stable.
As a preference, the first and second liquid crystal compositions are,
the halogen element is any one or more of chlorine, bromine and fluorine;
the concentration of the halogen salt in the salt solution is 1-3 wt%.
The halogen elements generally comprise four kinds of fluorine, chlorine, bromine and iodine, but when the halogen elements are used for hydrothermal halogenation doping, the iodine element atom volume is larger, so that the doping difficulty is increased, and the doping mode is closer to the replacement doping mode like metal element doping modification, so that the doping effect is poorer, and the improvement of the high-temperature oxidation resistance is limited. Therefore, the doping effect by selecting chlorine, bromine and fluorine is better. When the concentration of the halogen salt is too high, a large amount of halogen salt is easily generated with the matrix component of the titanium-based alloy, the mechanical property of the titanium-based alloy is reduced, and when the concentration is too low, a good halogenation effect cannot be achieved.
As a preference, the first and second liquid crystal compositions are,
the salt solution contains soluble fluorine salt.
Compared with other halogen elements, the fluorine has the smallest doping difficulty, the high-temperature oxidation resistance generated after doping is improved most obviously, and the influence on the mechanical property of the titanium-based alloy is smallest.
As a preference, the first and second liquid crystal compositions are,
the soluble fluoride salt is ammonium fluoride.
The doping effect of ammonium fluoride is better than that of other fluorine salts.
As a preference, the first and second liquid crystal compositions are,
the titanium-based alloy is an aluminum-containing titanium-based alloy.
The aluminum-containing titanium-based alloy can also contain any one or more elements of niobium, nickel, chromium and silicon. The improvement of the high-temperature oxidation resistance of the aluminum-containing titanium-based alloy after treatment is more remarkable, and the titanium-based alloy is doped with elements of the titanium-aluminum alloy, and the experiment proves that the high-temperature oxidation resistance of the alloy after high-temperature fluorination treatment is remarkably improved.
As a preference, the first and second liquid crystal compositions are,
the hydrothermal treatment temperature is 120-200 ℃, and the time of primary hydrothermal treatment is 5-10 h.
The temperature and time ranges can basically achieve the aim of improving the high-temperature oxidation resistance of the titanium-based alloy.
As a preference, the first and second liquid crystal compositions are,
the hydrothermal treatment temperature is 140-180 ℃, and the time of primary hydrothermal treatment is 6-10 h.
After the hydrothermal treatment at the temperature and within the time range, the high-temperature oxidation resistance of the titanium-based alloy is improved remarkably, and the influence on the mechanical property of the titanium-based alloy is small.
As a preference, the first and second liquid crystal compositions are,
the hydrothermal treatment temperature is 150 ℃, and the time of primary hydrothermal treatment is 8 hours.
The titanium-based alloy obtained after hydrothermal treatment under the above conditions has better high-temperature oxidation resistance.
The invention has the beneficial effects that:
1) the high-temperature oxidation resistance of the titanium-based alloy can be effectively improved;
2) the problem of reduction of mechanical property of the titanium-based alloy can be avoided;
3) the treatment method is simple and efficient, has lower operation difficulty, lower cost, lower equipment requirement and higher treatment efficiency, and is more suitable for industrial production;
4) the shape of the titanium-based alloy is not limited, and the titanium-based alloy can be applied to the alloy treatment of any shape.
Drawings
FIG. 1 is an SEM representation of a titanium-based alloy specimen prepared in example 4;
FIG. 2 is a SEM representation of a titanium-based alloy coupon prepared in example 4;
FIG. 3 is a comparison of the results of the breaking strength tests for the samples of example 6;
FIG. 4 is a graph comparing the results of the flexural strength test on the samples of example 6;
FIG. 5 is a graph comparing the results of the breaking strength test for the samples of example 7;
FIG. 6 is a graph comparing the results of the flexural strength test of the sample of example 7.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
Firstly, carrying out conventional pretreatment on a titanium-based alloy: and (3) polishing a Ti-Al alloy sample (the atomic ratio of titanium to aluminum is 1:1) by using sand paper to remove surface oxides, then sequentially carrying out ultrasonic cleaning in acetone and ethanol for 10min, and finally carrying out blow-drying by using hot air to obtain the pretreated titanium-based alloy. Mixing ammonium fluoride, potassium fluoride and sodium fluoride according to a molar ratio of 10: 1: 2 at room temperature, stirring for 2h in deionized water to prepare a salt solution with the total halogen salt concentration of 2 wt%, soaking the pretreated titanium-based alloy in the salt solution, putting the titanium-based alloy and the salt solution into a stainless steel water heating kettle with a polytetrafluoroethylene lining together, putting the kettle into an oven, carrying out hydrothermal treatment for 6h at the temperature of 140 ℃, naturally cooling after the completion, washing with deionized water, and airing to obtain the titanium-aluminum alloy sample with the surface containing F. And then, the high-temperature oxidation resistance of the composite material is evaluated by adopting the weight gain of unit area after constant-temperature oxidation at 1000 ℃ for 100 hours, and the specific results are shown in table 1.
TABLE 1 experimental results for example 1 hydrothermally treated Ti-Al alloy and bare Ti-Al alloy.
Example 2
Firstly, carrying out conventional pretreatment on a titanium-based alloy: polishing a 3Ti-Al alloy sample (the atomic ratio of titanium to aluminum is 3:1) by using sand paper to remove surface oxides, then sequentially carrying out ultrasonic cleaning in acetone and ethanol for 10min, and finally carrying out blow-drying by using hot air to obtain the pretreated titanium-based alloy. Mixing ammonium fluoride, potassium fluoride and sodium fluoride according to a molar ratio of 20: 1.5: 2 at room temperature, stirring for 2 hours in deionized water to prepare a salt solution with the total halogen salt concentration of 2 wt%, soaking the pretreated titanium-based alloy in the salt solution, putting the titanium-based alloy and the salt solution into a stainless steel water heating kettle with a polytetrafluoroethylene lining together, putting the kettle into an oven, carrying out hydrothermal treatment for 10 hours at the temperature of 180 ℃, naturally cooling the titanium-based alloy after the hydrothermal treatment, washing the titanium-based alloy with the deionized water, and airing the titanium-based alloy to obtain a titanium-aluminum alloy sample with the surface containing F. And then, the high-temperature oxidation resistance of the composite material is evaluated by adopting the weight gain of unit area after constant-temperature oxidation at 1000 ℃ for 100 hours, and the specific results are shown in table 2.
TABLE 2 experimental results for example 2 hydrothermally treated 3Ti-Al alloy and bare 3Ti-Al alloy.
| Sample (I) | Weight gain mg/cm2 |
| Bare 3Ti-Al alloy | 58.17 |
| Heat treated 3Ti-Al alloy | 5.37 |
Example 3
Firstly, carrying out conventional pretreatment on a titanium-based alloy: polishing a 3Ti-Al alloy sample (the atomic ratio of titanium to aluminum is 3:1) by using sand paper to remove surface oxides, then sequentially carrying out ultrasonic cleaning in acetone and ethanol for 10min, and finally carrying out blow-drying by using hot air to obtain the pretreated titanium-based alloy. Mixing ammonium fluoride, potassium fluoride and sodium fluoride according to a molar ratio of 20: 1.5: dissolving the titanium-based alloy in the proportion of 1 in deionized water, stirring for 2 hours at room temperature to prepare a salt solution with the total halogen salt concentration of 2 wt%, soaking the pretreated titanium-based alloy in the salt solution, putting the titanium-based alloy and the salt solution into a stainless steel water heating kettle with a polytetrafluoroethylene lining together, putting the kettle into an oven, carrying out hydrothermal treatment for 10 hours at the temperature of 150 ℃, naturally cooling after the completion, washing with the deionized water, and airing to obtain a titanium-aluminum alloy sample with the surface containing F. And then, the high-temperature oxidation resistance of the composite material is evaluated by adopting the weight gain of unit area after constant-temperature oxidation at 1000 ℃ for 100 hours, and the specific results are shown in Table 3.
TABLE 3 experimental results for example 3 hydrothermally treated 3Ti-Al alloy and bare 3Ti-Al alloy.
| Sample (I) | Weight gain mg/cm2 |
| Bare 3Ti-Al alloy | 58.17 |
| Heat treated 3Ti-Al alloy | 2.35 |
Example 4
Firstly, carrying out conventional pretreatment on a titanium-based alloy: and (3) polishing a Ti-Al alloy sample (the atomic ratio of titanium to aluminum is 1:1) by using sand paper to remove surface oxides, then sequentially carrying out ultrasonic cleaning in acetone and ethanol for 10min, and finally carrying out blow-drying by using hot air to obtain the pretreated titanium-based alloy. Mixing ammonium fluoride, potassium fluoride and sodium fluoride according to a molar ratio of 10: 1: 2 at room temperature, stirring for 2h in deionized water to prepare a salt solution with the total halogen salt concentration of 2 wt%, soaking the pretreated titanium-based alloy in the salt solution, putting the titanium-based alloy and the salt solution into a stainless steel water heating kettle with a polytetrafluoroethylene lining together, putting the kettle into an oven, carrying out hydrothermal treatment for 8h at the temperature of 150 ℃, naturally cooling after the completion, washing with deionized water, and airing to obtain the titanium-aluminum alloy sample with the surface containing F. And then, the high-temperature oxidation resistance of the composite material is evaluated by adopting the weight gain of unit area after constant-temperature oxidation at 1000 ℃ for 100 hours, and specific results are shown in table 4. The titanium-aluminum alloy sample prepared in this example was subjected to SEM characterization, and the characterization results are shown in fig. 1 and 2.
TABLE 4 experimental results for example 4 hydrothermally treated Ti-Al alloys and bare Ti-Al alloys.
| Sample (I) | Weight gain mg/cm2 |
| Bare TiAl alloy | 49.74 |
| Heat treated TiAl alloys | 0.94 |
Example 5
The specific procedure was the same as in example 4, except that the titanium-aluminum alloy substrate used and the hydrothermal frequency were changed, the high-temperature oxidation resistance evaluation was the same as in example 1, and the experimental results are shown in Table 5.
Table 5: and (5) experimental results after treatment of different titanium-based alloy carriers.
Example 6
The specific steps are the same as example 4, except that the hydrothermal treatment time is changed to 3h, 5h, 6h, 7h, 8h, 9h and 10h respectively. The high temperature oxidation resistance was evaluated in the same manner as in example 1, and the results are shown in Table 6.
Table 6: experimental results after treatment with different heat treatment times.
| Sample (I) | Weight gain mg/ |
| 3h | 31.62 |
| 5h | 10.37 |
| 6h | 9.86 |
| 7h | 3.55 |
| 8h | 0.94 |
| 9h | 1.97 |
| 10h | 4.52 |
Example 7
The specific procedure was the same as in example 4, except that the hydrothermal treatment temperature was changed to 120 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C and 200 deg.C, respectively. The high temperature oxidation resistance was evaluated in the same manner as in example 1, and the results are shown in Table 7.
Table 7: and (5) experimental results after treatment at different heat treatment temperatures.
| Sample (I) | Weight gain mg/ |
| 120℃ | 3.14 |
| 140℃ | 2.02 |
| 150℃ | 0.94 |
| 160℃ | 1.26 |
| 170℃ | 2.17 |
| 180℃ | 3.51 |
| 200℃ | 4.22 |
Example 8
The procedure was as in example 4, except that the halogen salt and salt solution concentrations were varied. The high temperature oxidation resistance was evaluated in the same manner as in example 1, and the results are shown in Table 8.
Table 8: the experimental results after treatment of different concentrations of halogen salt and salt solution.
| Halogen salt (molar ratio/salt solution concentration) | Weight gain mg/cm2 |
| Ammonium fluoride, potassium fluoride and sodium fluoride (10: 1: 2/0.2 wt%) | 0.94 |
| Ammonium fluoride, potassium fluoride and sodium fluoride (10: 1: 2/0.1 wt%) | 1.42 |
| Ammonium fluoride, potassium fluoride and sodium fluoride (10: 1: 2/0.3 wt%) | 0.89 |
| Ammonium fluoride (1/0.2 wt%) | 0.96 |
| Sodium fluoride (1/0.2 wt%) | 1.07 |
| Sodium bromide (1/0.2 wt%) | 1.32 |
| Sodium chloride (1/0.2 wt%) | 1.16 |
And (3) testing mechanical properties:
the titanium base alloys treated in examples 6 and 7 were tested for mechanical properties, all of which were recorded as the mean of ten standard samples, and the mechanical properties were measured by using the test results of bare Ti-Al alloy as a reference line and the test samples prepared in example 1 of CN108486631A patent as a comparison sample. Wherein the graph comparing the breaking strength test results of example 6 with the reference line and the comparative sample is shown in FIG. 3, the graph comparing the breaking strength test results is shown in FIG. 4, the graph comparing the breaking strength test results of example 7 with the reference line and the comparative sample is shown in FIG. 5, and the graph comparing the breaking strength test results is shown in FIG. 6. As is obvious from the figure, after hydrothermal halogenation, the mechanical property retention rate of the titanium-based alloy is higher, and is basically close to that of the untreated titanium-based alloy particularly at the temperature of 140-180 ℃ within 6-8 h.
Claims (8)
1. A method for improving the high-temperature oxidation resistance of titanium-based alloy by hydrothermal treatment is characterized in that,
the method comprises the following steps:
preparing a salt solution by using halogen salt containing halogen elements, placing the titanium-based alloy in the salt solution, placing the titanium-based alloy in a sealed reactor for at least one time of hydrothermal treatment, and finally cooling, cleaning and drying.
2. The method for improving the high-temperature oxidation resistance of the titanium-based alloy by hydrothermal treatment according to claim 1,
the halogen element is any one or more of chlorine, bromine and fluorine;
the concentration of the halogen salt in the salt solution is 1-3 wt%.
3. The method for improving the high-temperature oxidation resistance of the titanium-based alloy by hydrothermal treatment according to claim 1 or 2,
the salt solution contains soluble fluorine salt.
4. The method of claim 3, wherein the soluble fluoride salt is ammonium fluoride.
5. The method of claim 1, wherein the titanium-based alloy is an aluminum-containing titanium-based alloy.
6. The method for improving the high-temperature oxidation resistance of the titanium-based alloy through the hydrothermal treatment according to claim 1, wherein the hydrothermal treatment temperature is 120-200 ℃, and the time of the primary hydrothermal treatment is 5-10 h.
7. The method for improving the high-temperature oxidation resistance of the titanium-based alloy through the hydrothermal treatment according to claim 6, wherein the hydrothermal treatment temperature is 140-180 ℃, and the time of the primary hydrothermal treatment is 6-10 h.
8. The method for improving the high-temperature oxidation resistance of the titanium-based alloy by virtue of the hydrothermal treatment, as recited in claim 7, wherein the hydrothermal treatment temperature is 150 ℃, and the time of the primary hydrothermal treatment is 8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911108371.0A CN111206241B (en) | 2019-11-13 | 2019-11-13 | Method for improving high-temperature oxidation resistance of titanium-based alloy through hydrothermal treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911108371.0A CN111206241B (en) | 2019-11-13 | 2019-11-13 | Method for improving high-temperature oxidation resistance of titanium-based alloy through hydrothermal treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111206241A true CN111206241A (en) | 2020-05-29 |
| CN111206241B CN111206241B (en) | 2021-11-23 |
Family
ID=70785050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911108371.0A Active CN111206241B (en) | 2019-11-13 | 2019-11-13 | Method for improving high-temperature oxidation resistance of titanium-based alloy through hydrothermal treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111206241B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114657501A (en) * | 2022-02-28 | 2022-06-24 | 太原理工大学 | Method for improving high-temperature oxidation resistance of high Nb-TiAl alloy |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101660190A (en) * | 2009-09-18 | 2010-03-03 | 西北有色金属研究院 | Preparation method of titanium and titanium alloy surface black protective film for surgical implantation |
| KR20100030761A (en) * | 2008-09-11 | 2010-03-19 | 한국기초과학지원연구원 | Method for preparation of monodispersed anatase titanium dioxide nanoparticle |
| US20100136506A1 (en) * | 2007-07-19 | 2010-06-03 | Osteophil Co., Ltd. | Method of fabricating implant with improved surface properties and implant fabricated by the same method |
| CN105543798A (en) * | 2015-12-31 | 2016-05-04 | 浙江大学 | Method for improving high-temperature oxidization resistance of titanium-based alloy |
| CN106423227A (en) * | 2016-10-31 | 2017-02-22 | 天津大学 | Synthesis method of Br-doped TiO2 hollow spherical nanomaterial |
| CN106906505A (en) * | 2016-12-31 | 2017-06-30 | 浙江工业大学 | It is a kind of that the method that ceramic coating improves titanium-base alloy high temperature oxidation resistance is obtained based on halide effect and pretreatment |
| CN107419233A (en) * | 2017-06-26 | 2017-12-01 | 南京航空航天大学 | A kind of titanium aluminium base alloy surface protection coating and preparation method thereof |
| CN108486631A (en) * | 2018-03-13 | 2018-09-04 | 浙江工业大学 | A method of improving titanium-base alloy resistance to high temperature oxidation |
-
2019
- 2019-11-13 CN CN201911108371.0A patent/CN111206241B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100136506A1 (en) * | 2007-07-19 | 2010-06-03 | Osteophil Co., Ltd. | Method of fabricating implant with improved surface properties and implant fabricated by the same method |
| KR20100030761A (en) * | 2008-09-11 | 2010-03-19 | 한국기초과학지원연구원 | Method for preparation of monodispersed anatase titanium dioxide nanoparticle |
| CN101660190A (en) * | 2009-09-18 | 2010-03-03 | 西北有色金属研究院 | Preparation method of titanium and titanium alloy surface black protective film for surgical implantation |
| CN105543798A (en) * | 2015-12-31 | 2016-05-04 | 浙江大学 | Method for improving high-temperature oxidization resistance of titanium-based alloy |
| CN106423227A (en) * | 2016-10-31 | 2017-02-22 | 天津大学 | Synthesis method of Br-doped TiO2 hollow spherical nanomaterial |
| CN106906505A (en) * | 2016-12-31 | 2017-06-30 | 浙江工业大学 | It is a kind of that the method that ceramic coating improves titanium-base alloy high temperature oxidation resistance is obtained based on halide effect and pretreatment |
| CN107419233A (en) * | 2017-06-26 | 2017-12-01 | 南京航空航天大学 | A kind of titanium aluminium base alloy surface protection coating and preparation method thereof |
| CN108486631A (en) * | 2018-03-13 | 2018-09-04 | 浙江工业大学 | A method of improving titanium-base alloy resistance to high temperature oxidation |
Non-Patent Citations (4)
| Title |
|---|
| FRAYRET, C等: ""Development of a model for the anodic behavior of T60 titanium in chlorinated and oxygenated aqueous media. Application to the specific conditions of hydrothermal oxidation (1 MPa < pressure < 30 MPa, 20 degrees C < temperature < 400 degrees C)"", 《ELECTROCHIMICA ACTA》 * |
| MO, MH 等: ""Improvement of the high temperature oxidation resistance of Ti-50Al at 1000 degrees C by anodizing in ethylene glycol/BmimPF(6) solution"", 《SURFACE & COATINGS TECHNOLOGY》 * |
| NEVE, S等: ""High temperature oxidation resistance of fluorine-treated TiAl alloys: Chemical vs. ion beam fluorination techniques"", 《NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEAM INTERACTIONS WITH MATERIALS AND ATOMS》 * |
| 夏俊捷等: "基于卤素效应的阳极氧化技术提高Ti48Al5Nb合金抗高温氧化性能", 《中国腐蚀与防护学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114657501A (en) * | 2022-02-28 | 2022-06-24 | 太原理工大学 | Method for improving high-temperature oxidation resistance of high Nb-TiAl alloy |
| CN114657501B (en) * | 2022-02-28 | 2023-10-27 | 太原理工大学 | Method for improving high-temperature oxidation resistance of high-Nb-TiAl alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111206241B (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111235518B (en) | Method for improving high-temperature oxidation resistance of titanium-based alloy through high-temperature fluorination treatment | |
| KR20090020496A (en) | Anodized aluminum alloy material having both durability and low polluting property | |
| CN107058926B (en) | A method of reduction zircaloy plate texture is handled by phase transformation | |
| CN108588771B (en) | Composite ceramic coating containing noble metal intermediate layer and preparation process thereof | |
| CN111206241B (en) | Method for improving high-temperature oxidation resistance of titanium-based alloy through hydrothermal treatment | |
| CN107217227A (en) | A kind of method for improving nickel-base alloy antioxygenic property | |
| CN113278850B (en) | High-temperature-resistant titanium alloy protective coating and preparation method thereof | |
| CN109022921B (en) | Application of the Ni-Nb bianry alloy in the corrosion of anti-tellurium | |
| CN107937874A (en) | A kind of method for preparing Pt Al high-temperature protection coatings on niobium alloy surface | |
| CN114540732A (en) | Method for synergistically obtaining low sigma grain boundaries and saw-tooth grain boundaries | |
| CN106906505B (en) | A method of ceramic coating is obtained based on halide effect and pretreatment and improves titanium-base alloy high temperature oxidation resistance | |
| CN110306216B (en) | Active element Re modified beta- (Ni, Pt) -Al coating and preparation process thereof | |
| CN112899756B (en) | Preparation method of titanium alloy SiOC coating | |
| CN115369354B (en) | Nickel-based superalloy material and preparation method and application of surface coating thereof | |
| CN113278973A (en) | Titanium-based alloy part with nickel-modified silicon-based protective coating and preparation method thereof | |
| CN114737229A (en) | Method for preparing platinum modified aluminide coating on surface of single crystal high-temperature alloy | |
| CN108517551B (en) | Novel silicon-aluminum coating and preparation process thereof | |
| CN111057993B (en) | Method for improving tellurium corrosion resistance of alloy material for molten salt reactor and alloy part | |
| CN114855135B (en) | CeO on surface of metal material 2 Composite film and preparation method thereof | |
| CN111607758A (en) | Method for improving service temperature of titanium-based alloy based on fluorination treatment | |
| CN106835227B (en) | A method of titanium-base alloy high temperature oxidation resistance is improved based on halide effect and ceramic coating | |
| CN112877752B (en) | Preparation method of titanium alloy SiOC composite coating | |
| CN111826003B (en) | Coating material for hard alloy and preparation method thereof | |
| JPS6035992B2 (en) | Al coating method for Ni alloy | |
| CN115852326B (en) | Preparation method of liquid lead/lead bismuth corrosion resistant FeCrAlYTi high-entropy alloy coating |
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 |