CN112111744A - Fluoride-free pickling method for titanium alloy - Google Patents
Fluoride-free pickling method for titanium alloy Download PDFInfo
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- CN112111744A CN112111744A CN202011000099.7A CN202011000099A CN112111744A CN 112111744 A CN112111744 A CN 112111744A CN 202011000099 A CN202011000099 A CN 202011000099A CN 112111744 A CN112111744 A CN 112111744A
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 43
- 238000005554 pickling Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 38
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 20
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 20
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 20
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 230000000171 quenching effect Effects 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000007605 air drying Methods 0.000 claims abstract description 7
- 238000000861 blow drying Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 24
- 238000005266 casting Methods 0.000 abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000007796 conventional method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
- 208000002599 Smear Layer Diseases 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 229910003080 TiO4 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003110 molding sand Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007447 staining method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/28—Cleaning or pickling metallic material with solutions or molten salts with molten salts
- C23G1/32—Heavy metals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention provides a fluorine-free pickling method for titanium alloy, which sequentially comprises the following steps: cutting the titanium alloy into strips of 20-30mm, removing oil and drying; uniformly mixing sodium hydroxide and sodium nitrate, heating to 400-500 ℃, then placing the dried sample into molten salt for treatment for 2-3min, taking out the sample, quenching in water, cooling, and drying to obtain an intermediate sample; adding oxalic acid into boiling water, adding the intermediate sample, treating at 90-100 ℃ for 20-30min until the surface is silvery white, and sequentially cleaning with clear water and air drying to finish the fluorine-free pickling of the titanium alloy. The method does not use a fluorine-containing chemical reagent in the acid cleaning process, can remove an alpha-stained layer on the surface of the titanium alloy, is also suitable for castings with complex structures, and effectively solves the problems of large potential safety hazard, high operation and maintenance cost, large environmental pollution and the like in the conventional method for cleaning hydrofluoric acid.
Description
Technical Field
The invention belongs to the technical field of material surface treatment, and particularly relates to a fluorine-free acid pickling method for a titanium alloy.
Background
In the process of titanium alloy casting, sand andthe casting solution reacts, elements (mainly O, H, N, Zr) in the molding sand enter into the surface of the casting to form an 'alpha' contamination layer at high temperature, and the hard and brittle 'alpha' contamination layer is not beneficial to further processing or using the titanium casting. The method of alkali washing and acid washing is commonly adopted in China to remove the alpha fouling layer of the titanium alloy casting. In the acid cleaning, a hydrofluoric acid and nitric acid aqueous solution (5-7% hydrofluoric acid + 30-40% nitric acid + residual water) is generally used, and the chemical reaction formula is as follows: 3Ti +4HNO3+12HF→3TiF4+8H2O+4NO。
But hydrofluoric acid is a chemical reagent which is difficult to control and has strong poison to skin and respiratory tract, and has larger potential safety hazard in environmental protection in the using process. Due to the danger of hydrofluoric acid, enterprises such as 621 th and 725 th in China, northwest colored hospitals and Zunyi titanium factories all adopt a closed pickling line, complete safety protection equipment and waste liquid treatment equipment, so that the safety and environmental protection of pickling operation are guaranteed, but the cost of establishment, operation and maintenance is huge. There is an urgent need for a safe, efficient and environmentally friendly pickling method.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a fluorine-free acid washing method for titanium alloy, wherein a fluorine-containing chemical reagent is not used in the acid washing process, an alpha-stained layer on the surface of the titanium alloy can be removed, the method is also suitable for castings with complex structures, and the problems of high potential safety hazard, high operation and maintenance cost, high environmental pollution and the like in hydrofluoric acid washing in the prior art are effectively solved.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the method for pickling the titanium alloy without the fluorine comprises the following steps in sequence:
(1) cutting the titanium alloy into strips of 20-30mm, removing oil and drying;
(2) uniformly mixing sodium hydroxide and sodium nitrate, heating to 400-500 ℃, then placing the dried sample obtained in the step (1) into molten salt for treatment for 2-3min, taking out the sample, quenching in water, cooling, and blow-drying to obtain an intermediate sample;
(3) and (3) adding oxalic acid into boiling water, then adding the intermediate sample obtained in the step (2), treating at the temperature of 90-100 ℃ for 20-30min until the surface is silvery white, and sequentially cleaning with clear water and air-drying to finish the fluorine-free pickling of the titanium alloy.
Further, in the step (1), the titanium alloy is ZTC 4.
Further, in the step (2), the mass ratio of the sodium hydroxide to the sodium nitrate is 340-.
Further, in the step (2), the mass ratio of the sodium hydroxide to the sodium nitrate is 350: 50.
Further, in the step (2), the temperature is raised to 450 ℃ after the sodium hydroxide and the sodium nitrate are uniformly mixed.
Further, in the step (3), the concentration of oxalic acid added to the boiling water is 20-40 wt%.
Further, in the step (3), the treatment is carried out at a temperature of 100 ℃ for 25 min.
In summary, the invention has the following advantages:
1. the method does not use a fluorine-containing chemical reagent in the acid cleaning process, can remove an alpha-stained layer on the surface of the titanium alloy, reveals metallic luster, conceals visible crystal grains, is also suitable for castings with complex structures, and effectively solves the problems of large potential safety hazard, high operation and maintenance cost, large environmental pollution and the like in the conventional method for cleaning hydrofluoric acid.
2. Firstly, cutting titanium alloy, removing oil and drying, decomposing and stripping an oxide layer on the surface of the titanium alloy by using molten sodium hydroxide and molten sodium nitrate after pretreatment is finished, wherein the chemical mode is as follows:
TiO2+4NaOH→Na4TiO4+2H2O；
Ti+4NaOH+O→2Na4TiO3+2H2；
the titanium oxide layer on most surface is effectively removed, and then the titanium alloy is placed in a boiling oxalic acid aqueous solution, so that the corrosion speed of titanium can be greatly increased by the boiling oxalic acid solution until the surface of the titanium alloy is white, the metallic luster is exposed, and crystal grains are hidden and visible.
3. The boiling oxalic acid solution is pickled to achieve the traditional effect of pickling with the fluorine-containing reagent, most of the 'alpha' contamination layers can be removed, and the residual thickness is smaller. Because the method does not adopt a fluorine-containing reagent, the safety is higher, the problem of greater environmental pollution can not be caused, special safety protection equipment is not needed, the operation and maintenance cost during acid washing is reduced, and the method is convenient to popularize and use.
Drawings
FIG. 1 is a schematic external view of a finished part according to example 3;
FIG. 2 is a schematic view showing the appearance of the "α" stained layer of the finished part of example 3;
FIG. 3 is a graph showing the corrosion rate of oxalic acid solution to titanium metal at different temperatures and concentrations;
FIG. 4 shows the appearance of different samples;
FIG. 5 is a gold phase diagram of various samples;
FIG. 6 is a graph of the "α" stain layer thickness for different samples;
FIG. 7 shows the results of microhardness measurements of different samples from the surface to the core.
Detailed Description
Example 1
A fluorine-free pickling method for titanium alloy sequentially comprises the following steps:
(1) cutting the ZTC4 casting into 20mm strips, and deoiling and drying;
(2) uniformly mixing sodium hydroxide and sodium nitrate, heating to 400 ℃, then placing the dried sample obtained in the step (1) into molten salt for treatment for 2min, taking out the sample, quenching in water, cooling, and blow-drying to obtain an intermediate sample; the mass ratio of the sodium hydroxide to the sodium nitrate is 340: 40;
(3) and (3) adding oxalic acid into boiling water, then adding the intermediate sample obtained in the step (2), treating at 90 ℃ for 20min until the surface is silvery white, and sequentially cleaning with clear water and air-drying to finish the fluorine-free pickling of the titanium alloy.
Example 2
A fluorine-free pickling method for titanium alloy sequentially comprises the following steps:
(1) cutting a ZTC4 casting into 23mm strips, and deoiling and drying;
(2) uniformly mixing sodium hydroxide and sodium nitrate, heating to 430 ℃, then placing the dried sample obtained in the step (1) into molten salt for treatment for 2min, taking out the sample, quenching in water, cooling, and blow-drying to obtain an intermediate sample; the mass ratio of the sodium hydroxide to the sodium nitrate is 345: 45;
(3) and (3) adding oxalic acid into boiling water, then adding the intermediate sample obtained in the step (2), treating at the temperature of 93 ℃ for 24min until the surface is silvery white, and sequentially cleaning with clear water and air-drying to finish the fluorine-free pickling of the titanium alloy.
Example 3
A fluorine-free pickling method for titanium alloy sequentially comprises the following steps:
(1) cutting a ZTC4 casting into 25mm strips, and deoiling and drying;
(2) uniformly mixing sodium hydroxide and sodium nitrate, heating to 450 ℃, then placing the dried sample obtained in the step (1) into molten salt for treatment for 3min, taking out the sample, quenching in water, cooling, and blow-drying to obtain an intermediate sample; the mass ratio of the sodium hydroxide to the sodium nitrate is 350: 50;
(3) and (3) adding oxalic acid into boiling water, then adding the intermediate sample obtained in the step (2), treating at 100 ℃ for 25min until the surface is silvery white, and sequentially cleaning with clear water and air-drying to finish the fluorine-free pickling of the titanium alloy.
Example 4
A fluorine-free pickling method for titanium alloy sequentially comprises the following steps:
(1) cutting a ZTC4 casting into 30mm strips, and deoiling and drying;
(2) uniformly mixing sodium hydroxide and sodium nitrate, heating to 500 ℃, then placing the dried sample obtained in the step (1) into molten salt for treatment for 3min, taking out the sample, quenching in water, cooling, and blow-drying to obtain an intermediate sample; the mass ratio of the sodium hydroxide to the sodium nitrate is 360: 60;
(3) and (3) adding oxalic acid into boiling water, then adding the intermediate sample obtained in the step (2), treating at 100 ℃ for 30min until the surface is silvery white, and sequentially cleaning with clear water and air-drying to finish fluoride-free pickling of the titanium alloy.
The titanium alloy was pickled by the fluorine-free pickling method shown in example 3, and the appearance of the finished product was as shown in FIG. 1, and the observation and measurement of the "α" smear layer were performed by the metallographic staining method as shown in FIG. 2.
As can be seen from FIGS. 1-2, the thickness of the "α" contamination layer was less than 10 μm, and the pickling effect achieved the desired goal.
Comparative example 1
A fluorine-free pickling method for titanium alloy sequentially comprises the following steps:
(1) cutting a ZTC4 casting into 25mm strips, and deoiling and drying;
(2) uniformly mixing sodium hydroxide and sodium nitrate, heating to 450 ℃, then placing the dried sample obtained in the step (1) into molten salt for treatment for 3min, taking out the sample, quenching in water, cooling, and blow-drying to obtain an intermediate sample; the mass ratio of the sodium hydroxide to the sodium nitrate is 350: 50;
(3) and (3) putting the intermediate sample obtained in the step (2) into hydrofluoric acid and nitric acid aqueous solution (prepared by mixing hydrofluoric acid, nitric acid and water according to the volume ratio of 1:7: 12) for treatment for 7min, and sequentially cleaning with clear water and drying in the air to finish the fluorine-free pickling of the titanium alloy.
Experimental example 1
The experiment was conducted in accordance with the fluorine-free pickling method of titanium alloy shown in example 3, and the pickling was conducted in step (3) with oxalic acid solutions of different concentrations at different temperatures (25 ℃, 60 ℃ and 100 ℃) respectively, and the corrosion rates thereof were measured, and the results are shown in FIG. 3.
As can be seen from fig. 3, as the etching temperature increases, the etching rate of the oxalic acid solution to the metallic titanium increases greatly. The oxalic acid solution concentration can greatly accelerate the corrosion speed of titanium at 100 ℃, wherein the corrosion speed of the oxalic acid solution with the concentration of 25 wt% on the titanium metal is approximately equal to 20% of the corrosion speed of the traditional pickling solution (the hydrofluoric acid and nitric acid aqueous solution: hydrofluoric acid, nitric acid and water are mixed according to the volume ratio of 1:7: 12) on the titanium metal at room temperature. Further, considering that water in the solution evaporates relatively rapidly at 100 ℃ and the concentration of the oxalic acid solution changes, it is considered to directly perform pickling with a saturated aqueous oxalic acid solution (concentration of about 40 wt%) in a boiling state.
Experimental example 2
Respectively obtaining an original sample, a sample after acid pickling in example 3 and a sample after acid pickling in comparative example 1, wherein the appearance and the appearance are respectively shown in figure 4; in FIG. 4, a, b and c are the appearance and appearance of the original sample, the sample after acid cleaning of example 3 and the sample after acid cleaning of comparative example 1.
As can be seen from fig. 4, after the original sample is treated by the two treatment methods, the oxide layer is removed from the surface of the sample, the sample presents metallic luster, and the crystal grains are invisible, and the appearance of the sample treated by the two treatment methods can meet the pickling requirement; but the flatness of the sample obtained by the invention is higher.
Experimental example 3
Corroding the original sample, the sample after acid pickling in the example 3 and the sample after acid pickling in the comparative example 1 by using a dyeing reagent, and obtaining metallographic pictures of the samples, wherein the results are shown in a figure 5; in FIG. 5, a, b and c are the gold phase diagrams of the original sample, the sample after acid washing of example 3 and the sample after acid washing of comparative example 1. The thickness of the "α" stain layer of the stained specimen was also measured directly using a MeF3 research-grade metallographic microscope, and the results are shown in FIG. 6.
As can be seen from FIG. 5, the texture of the normal area of TC4 cast was yellowish brown, and the "α" stained layer was bright white. The sample obtained by the acid washing method can clearly display the condition of an alpha dirt layer on the edge, is convenient for measuring the thickness, and can avoid misjudgment on the alpha phase converted from the original beta crystal grains by dyeing.
As can be seen from fig. 6, the "α" stain layers of the samples treated in example 3 and comparative example 1 were thinner than the original samples, but were partially left, and the residual thickness of the "α" stain layer of the sample after the fluorine-free pickling method provided in example 3 was smaller. The above results indicate that the conventional method (hydrofluoric acid-nitric acid aqueous solution: hydrofluoric acid, nitric acid and water mixed at a volume ratio of 1:7: 12) has disadvantages and cannot find the residual "alpha" stain layer on the surface of the ZTC4 casting.
Experimental example 4
The microhardness from the surface to the inside of three samples (original sample, sample after acid cleaning in example 3 and sample after acid cleaning in comparative example 1) is respectively measured by adopting an HXD-1000TMB/LCD type microhardness tester; the first hardness test point was measured every 0.01mm from the edge, and the results are shown in FIG. 7.
As can be seen from FIG. 7, the sample surface treated by the fluorine-free pickling method had no "α" stain layer, the thickness of the "α" stain layer on the sample surface treated by the method shown in comparative example 1 was 0.02mm, and the hardness measurement result was substantially identical to the metallographic dyeing result in Experimental example 3.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (8)
1. The fluorine-free acid cleaning method for the titanium alloy is characterized by sequentially comprising the following steps of:
(1) cutting the titanium alloy into strips of 20-30mm, removing oil and drying;
(2) uniformly mixing sodium hydroxide and sodium nitrate, heating to 400-500 ℃, then placing the dried sample obtained in the step (1) into molten salt for treatment for 2-3min, taking out the sample, quenching in water, cooling, and blow-drying to obtain an intermediate sample;
(3) and (3) adding oxalic acid into boiling water, then adding the intermediate sample obtained in the step (2), treating at the temperature of 90-100 ℃ for 20-30min until the surface is silvery white, and sequentially cleaning with clear water and air-drying to finish the fluorine-free pickling of the titanium alloy.
2. The fluorine-free pickling method of a titanium alloy according to claim 1, wherein in the step (1), the titanium alloy is ZTC 4.
3. The fluorine-free pickling method for titanium alloy as claimed in claim 1, wherein in the step (2), the mass ratio of the sodium hydroxide to the sodium nitrate is 340-360: 40-60.
4. The fluorine-free pickling method for titanium alloy according to claim 3, wherein in the step (2), the mass ratio of the sodium hydroxide to the sodium nitrate is 350: 50.
5. The fluorine-free pickling method of the titanium alloy according to claim 1, wherein in the step (2), the temperature is raised to 450 ℃ after the sodium hydroxide and the sodium nitrate are mixed uniformly.
6. The fluorine-free pickling method of a titanium alloy according to claim 1, wherein in the step (3), the oxalic acid is added to the boiling water to a concentration of 20 to 40 wt%.
7. The fluorine-free pickling method of a titanium alloy according to claim 1, wherein in the step (3), the oxalic acid is added to the boiling water to a concentration of 30 wt%.
8. The fluorine-free pickling method of a titanium alloy according to claim 1, wherein in the step (3), the treatment is carried out at a temperature of 100 ℃ for 25 minutes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09157872A (en) * | 1995-12-06 | 1997-06-17 | Kobe Steel Ltd | Titanium or titanium alloy member having beautiful surface and production thereof |
| CN101709474A (en) * | 2009-11-26 | 2010-05-19 | 攀钢集团江油长城特殊钢有限公司 | Alkali-acid washing method for titanium alloy |
| CN102286734A (en) * | 2011-06-22 | 2011-12-21 | 沈阳理工大学 | Pretreatment technology of surface metal plating of titanium alloy and metal plating method |
| CN103114293A (en) * | 2013-03-08 | 2013-05-22 | 沈阳飞机工业（集团）有限公司 | Technology process for removing scale cinder in thermal forming of TC4 titanium alloy |
-
2020
- 2020-09-22 CN CN202011000099.7A patent/CN112111744A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09157872A (en) * | 1995-12-06 | 1997-06-17 | Kobe Steel Ltd | Titanium or titanium alloy member having beautiful surface and production thereof |
| CN101709474A (en) * | 2009-11-26 | 2010-05-19 | 攀钢集团江油长城特殊钢有限公司 | Alkali-acid washing method for titanium alloy |
| CN102286734A (en) * | 2011-06-22 | 2011-12-21 | 沈阳理工大学 | Pretreatment technology of surface metal plating of titanium alloy and metal plating method |
| CN103114293A (en) * | 2013-03-08 | 2013-05-22 | 沈阳飞机工业（集团）有限公司 | Technology process for removing scale cinder in thermal forming of TC4 titanium alloy |
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