CN104073802A - Chemical milling solution for pure titanium, titanium alloys or titanium aluminium intermetallic compounds and application of chemical milling solution - Google Patents
Chemical milling solution for pure titanium, titanium alloys or titanium aluminium intermetallic compounds and application of chemical milling solution Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 155
- 238000003801 milling Methods 0.000 title claims abstract description 146
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 32
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 29
- 239000010936 titanium Substances 0.000 title claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 title claims description 5
- 239000004411 aluminium Substances 0.000 title claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 30
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 238000005260 corrosion Methods 0.000 claims abstract description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims description 20
- -1 ammonium hexafluorophosphate Chemical compound 0.000 claims description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 5
- 235000010234 sodium benzoate Nutrition 0.000 claims description 5
- 239000004299 sodium benzoate Substances 0.000 claims description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 5
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 4
- KHADWTWCQJVOQO-UHFFFAOYSA-N zinc;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Zn+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KHADWTWCQJVOQO-UHFFFAOYSA-N 0.000 claims description 4
- BRRSNXCXLSVPFC-UHFFFAOYSA-N 2,3,4-Trihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1O BRRSNXCXLSVPFC-UHFFFAOYSA-N 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 3
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 3
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 3
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 claims description 3
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 3
- 229940080350 sodium stearate Drugs 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229960004274 stearic acid Drugs 0.000 claims description 3
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000003746 surface roughness Effects 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 56
- 230000007547 defect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 238000003754 machining Methods 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004349 Ti-Al Inorganic materials 0.000 description 2
- 229910021330 Ti3Al Inorganic materials 0.000 description 2
- 229910004692 Ti—Al Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JWJKTSDFCKHJRC-UHFFFAOYSA-N hydrogen peroxide nitric acid hydrofluoride Chemical compound F.OO.O[N+]([O-])=O JWJKTSDFCKHJRC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention relates to the field of chemical milling processing and in particular relates to a chemical milling solution which can be used for the materials prone to hydrogen embrittlement, such as pure titanium, titanium alloys or titanium aluminum intermetallic compounds and the like, and a chemical milling method. The chemical milling solution comprises the following components: 20-350g/L of hydrofluoric acid, 150-750g/L of nitric acid, 50-550g/L of hydrogen peroxide, 0.5-20g/L of corrosion inhibitors, 5-200g/L of urea, 0.5-25g/L of surfactants, 0-100g/L of metal ions and the balance of water. The chemical milling method comprises the following steps: immersing metal materials subjected to pretreatment in the chemical milling solution, carrying out chemical milling processing on the materials at 35-75 DEG C, taking out the parts when achieving the chemical milling depth and washing out the chemical milling solution on the surfaces of the parts with clear water. The chemical milling solution and chemical milling processing method provided by the invention have the beneficial effects that the hydrogen absorption capacities of the metal materials prone to hydrogen embrittlement, such as titanium alloys and the like during chemical milling processing can be effectively controlled; hydrogen embrittlement harms to the parts can be reduced; the treated parts have good surface roughness and low hydrogen contents; and the whole chemical milling process is simple to operate.
Description
Technical Field
The invention relates to the field of chemical milling, in particular to a chemical milling solution and a chemical milling method for materials which are easy to generate hydrogen embrittlement, such as pure titanium, titanium alloy or titanium-aluminum intermetallic compounds.
Background
Chemical milling, also called corrosion machining, is a machining method that utilizes chemical solutions such as acid, alkali, salt, etc. to generate chemical reactions on metals, so as to dissolve the metals and change the size and shape (or surface properties) of a workpiece.
The chemical milling processing is not limited by the hardness and the strength of materials, the defects of stress, burrs and the like can not be generated in the processing process, the workpiece has no deformation, multiple surfaces and multiple pieces can be processed simultaneously, and the production efficiency is high. The method is commonly used for machining allowance of parts with complex shapes and thin plate parts, and the parts needing large-area surface layer milling are also commonly processed by a chemical milling method. The chemical milling processing has simple operation technology and high processing precision, and can be used for processing materials or shapes which are difficult to process by a processing machine.
Chemical milling of titanium alloy has become a reliable processing method for forming aerospace parts, but one outstanding problem in the chemical milling process of titanium alloy parts is that the chemical milling under an acidic solution can increase the hydrogen content of the parts, and especially the hydrogen absorption is more prominent in alpha + beta type and beta type titanium alloys. The data report that the hydrogen content in titanium and titanium alloy is generally not higher than 0.0125% -0.015%, otherwise, obvious hydrogen embrittlement phenomenon occurs, and the material has cracks and fractures in subsequent processing and use.
The titanium-aluminum intermetallic compound material has small density and good high-temperature performance, can replace nickel-based high-temperature alloy with larger density in a certain temperature range, effectively realizes the weight reduction of parts, and is considered as a new generation of light high-temperature resistant structural material with the most application potential. But the room temperature plasticity is low, the hardness is high, and the processability is poor. The titanium-aluminum intermetallic compound with intrinsic brittleness needs to be more careful in the process of processing and using so as to prevent the hydrogen embrittlement phenomenon.
Disclosure of Invention
The invention aims to provide a chemical milling solution of pure titanium, titanium alloy or titanium-aluminum intermetallic compound and application thereof, which greatly reduce the hydrogen absorption amount of the material in the chemical milling process, have the advantages of controllable chemical milling speed, good surface roughness, simple process control and the like, and can control the hydrogen content in parts within an allowable range without increasing a vacuum dehydrogenation process.
The technical scheme of the invention is as follows:
a chemical milling solution of pure titanium, titanium alloy or titanium-aluminum intermetallic compound comprises the following components: 20-350 g/L hydrofluoric acid, 150-750 g/L nitric acid, 50-550 g/L hydrogen peroxide, 0.5-20 g/L corrosion inhibitor, 5-200 g/L urea, 0.5-25 g/L surfactant, 0-180 g/L metal ions and the balance of water.
The corrosion inhibitor of the chemical milling solution of the pure titanium, the titanium alloy or the titanium-aluminum intermetallic compound is one or more than two of sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium metaphosphate, sodium polyphosphate, sodium dichromate, potassium dichromate, zinc dichromate, sodium chromate, potassium chromate, ammonium hexafluorophosphate, hexamethylenetetramine, benzoic acid, trihydroxybenzoic acid, thiourea, acridine, pyridine and furfural.
The chemical milling solution of the pure titanium, the titanium alloy or the titanium-aluminum intermetallic compound comprises one or more than two of sodium benzoate, linear alkyl benzene sodium sulfonate, sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, sodium glycocholate, dodecyl benzene sulfonic acid, sodium dodecyl benzene sulfonate, stearic acid, sodium stearate, alkylolamide, fatty alcohol-polyoxyethylene ether and alkylphenol polyoxyethylene ether as a surfactant.
In the chemical milling solution of the pure titanium, the titanium alloy or the titanium-aluminum intermetallic compound, the metal ions are titanium ions and/or aluminum ions, and are added in the form of powder or particles of metal, alloy or intermetallic compound respectively.
The application of the chemical milling solution of the pure titanium, the titanium alloy or the titanium-aluminum intermetallic compound comprises the following steps:
(1) removing dust and oil stains on the surface of a part needing chemical milling;
(2) immersing the cleaned parts in the chemical milling solution, carrying out chemical milling processing at 35-75 ℃, taking out the parts immediately after reaching the chemical milling depth, and cleaning with warm water at 40-50 ℃ to remove the residual chemical milling solution on the surface.
In the step (1), the chemical milling solution of pure titanium, titanium alloy or titanium-aluminum intermetallic compound is used for washing dust on the surface of parts by using clear water, washing surface oil stain by using ethanol, acetone or aviation gasoline, and then cleaning and drying by using clear water.
In the step (2), the chemical milling speed is 0.01-0.035 mm/min.
The invention has the advantages and beneficial effects that:
1. the titanium alloy or the titanium-aluminum intermetallic compound is a difficult-to-machine material, and the chemical milling method of the invention performs the later-stage machining and allowance adjustment of the parts of the material, and has the advantages of high production efficiency, high yield, low cost, simple operation and the like.
2. The titanium alloy or titanium-aluminum intermetallic compound is a material which is easy to absorb hydrogen and is easy to be brittle, the hydrogen content of the two materials, particularly alpha + beta type and beta type titanium-based materials, is greatly increased in the chemical milling process by the traditional chemical milling solution, the hydrogen absorption of the materials in the chemical milling process can be greatly reduced by the chemical milling solution provided by the invention, and the hydrogen content in parts can be controlled within an allowable range without increasing a vacuum dehydrogenation process.
3. Different from alloys, the titanium-aluminum intermetallic compound has 2-3 main elements, and the corrosion properties of the elements are greatly different.
In conclusion, the intermetallic Ti-Al compound is a material which is very easy to absorb hydrogen, the increase of hydrogen content has a great influence on the performance of the material, and basically all applications of the intermetallic Ti-Al material make strict requirements on the hydrogen content. The hydrofluoric acid is used as a corrosive agent, the nitric acid and the hydrogen peroxide are used as oxidants to effectively solve the problem of hydrogen absorption of the material in the chemical milling process, the formed hydrofluoric acid-nitric acid-hydrogen peroxide system can effectively control the increase of the hydrogen content in the material after chemical milling (the hydrogen content after chemical milling is only increased by 3-20 ppm), so that the hydrogen content of the compound between titanium and aluminum metals after chemical milling is greatly reduced, the smoothness and the surface roughness of the product are effectively improved by adding a proper corrosion inhibitor and a proper surfactant, the material is chemically milled at the temperature of 35-75 ℃, and the chemical milling speed is about 0.01-0.035 mm/min.
Detailed Description
The invention is suitable for chemical milling solution of titanium alloy and titanium-aluminum intermetallic compounds, and the chemical milling solution comprises the following components: 20-350 g/L hydrofluoric acid, 150-750 g/L nitric acid, 50-550 g/L hydrogen peroxide, 0.5-20 g/L corrosion inhibitor, 5-200 g/L urea, 0.5-25 g/L surfactant, 0-180 g/L metal ions and the balance of water. And (3) uniformly mixing the substances to prepare a chemical milling solution. Wherein,
the corrosion inhibitor is one or more than two of sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium metaphosphate, sodium polyphosphate, sodium dichromate, potassium dichromate, zinc dichromate, sodium chromate, potassium chromate, ammonium hexafluorophosphate, hexamethylenetetramine, benzoic acid, trihydroxybenzoic acid, thiourea, acridine, pyridine and furfural.
The surfactant is one or more of sodium benzoate, linear alkyl benzene sulfonic acid sodium salt, sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, sodium glycocholate, dodecylbenzene sulfonic acid, sodium dodecyl benzene sulfonate, stearic acid, sodium stearate, alkylolamide, fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.
The metal ions are titanium ions and/or aluminum ions, and are added in the form of powder or particles of metal, alloy or intermetallic compound, respectively.
Preferably, the invention is suitable for chemical milling solution of titanium alloy and titanium-aluminum intermetallic compound, and the chemical milling solution comprises the following components: 50-200 g/L of hydrofluoric acid, 200-600 g/L of nitric acid, 50-500 g/L of hydrogen peroxide, 1-10 g/L of corrosion inhibitor, 20-100 g/L of urea, 0.5-5 g/L of surfactant, 20-50 g/L of metal ions and the balance of water.
In the invention, hydrofluoric acid is used as a corrosive agent, nitric acid and hydrogen peroxide are used as oxidants, urea with a certain content is added to effectively reduce the generation of 'yellow smoke', and metal ions have the effect of aging solution and can improve the surface roughness of a chemical milling product.
The chemical milling method of the titanium alloy and the titanium-aluminum intermetallic compound by the chemical milling solution comprises the following steps:
(1) removing dust and oil stains on the surface of a part needing chemical milling;
(2) immersing the cleaned parts in a chemical milling solution, carrying out chemical milling processing at 35-75 ℃, taking out the parts immediately after reaching the chemical milling depth, and cleaning with warm water at 40-50 ℃ to remove the residual chemical milling solution on the surface;
in the step (1), the dust on the surface of the part is washed away by clean water, the greasy dirt on the surface is washed away by ethanol, acetone or aviation gasoline, and the part is cleaned and dried by clean water. In the step (2), the chemical milling speed is 0.01-0.035 mm/min.
The present invention is further illustrated by the following examples.
Example 1
The chemical milling solution comprises the following components: 50g/L of hydrofluoric acid, 200g/L of nitric acid, 150g/L of hydrogen peroxide, 1g/L of sodium polyphosphate, 10g/L of urea, 5g/L of sodium benzoate and the balance of water. And (3) uniformly mixing the substances to prepare a chemical milling solution.
Placing the chemical milling parts into aviation gasoline, soaking for 10-20 minutes to remove oil stains on the surfaces of the parts, then cleaning with warm water of 40-50 ℃ and drying, immersing the cleaned parts in the chemical milling solution of 40 ℃ until the size meets the requirement, taking out the parts, and cleaning with warm water of 40-50 ℃ to remove the residual chemical milling solution on the surfaces. The surface of the product after chemical milling has no defects of pits, ridge beams, intergranular corrosion and the like, the chemical milling rate is 0.011mm/min, and the hydrogen content after chemical milling is increased by 18 ppm.
Example 2
The chemical milling solution comprises the following components: 80g/L of hydrofluoric acid, 250g/L of nitric acid, 200g/L of hydrogen peroxide, 3g/L of sodium dihydrogen phosphate, 10g/L of urea, 5g/L of sodium benzoate and the balance of water. And (3) uniformly mixing the substances to prepare a chemical milling solution.
Placing the chemical milling parts into aviation gasoline, soaking for 10-20 minutes to remove oil stains on the surfaces of the parts, then cleaning with warm water of 40-50 ℃ and drying, immersing the cleaned parts in the chemical milling solution of 50 ℃ until the size meets the requirement, taking out the parts, and cleaning with warm water of 40-50 ℃ to remove the residual chemical milling solution on the surfaces. The surface of the product after chemical milling has no defects of pits, ridge beams, intergranular corrosion and the like, the chemical milling speed is 0.018mm/min, and the hydrogen content after chemical milling is increased by 17 ppm.
Example 3
The chemical milling solution comprises the following components: 100g/L of hydrofluoric acid, 500g/L of nitric acid, 150g/L of hydrogen peroxide, 10g/L of potassium chromate, 8g/L of urea, 5g/L of sodium dodecyl sulfate and the balance of water. And (3) uniformly mixing the substances to prepare a chemical milling solution.
And (2) placing the chemical milling parts into aviation gasoline, soaking for 10-20 minutes to remove oil stains on the surfaces of the parts, then cleaning with warm water of 40-50 ℃ and drying, immersing the cleaned parts in the chemical milling solution of 55 ℃ until the size meets the requirement, taking out the parts, and cleaning with warm water of 40-50 ℃ to remove the residual chemical milling solution on the surfaces. The surface of the product after chemical milling has no defects of pits, ridge beams, intergranular corrosion and the like, the chemical milling speed is 0.020mm/min, and the hydrogen content after chemical milling is increased by 6 ppm.
Example 4
The chemical milling solution comprises the following components: 100g/L of hydrofluoric acid, 350g/L of nitric acid, 300g/L of hydrogen peroxide, 5g/L of hexamethylenetetramine, 20g/L of urea, 2g/L of sodium dodecyl benzene sulfonate and the balance of water. And (3) uniformly mixing the substances to prepare a chemical milling solution.
Placing the chemical milling parts into aviation gasoline, soaking for 10-20 minutes to remove oil stains on the surfaces of the parts, then cleaning with warm water of 40-50 ℃ and drying, immersing the cleaned parts in the chemical milling solution of 50 ℃ until the size meets the requirement, taking out the parts, and cleaning with warm water of 40-50 ℃ to remove the residual chemical milling solution on the surfaces. The surface of the product after chemical milling has no defects of pits, ridge beams, intergranular corrosion and the like, the chemical milling speed is 0.018mm/min, and the hydrogen content after chemical milling is increased by 8 ppm.
Example 5
The chemical milling solution comprises the following components: 125g/L hydrofluoric acid, 750g/L nitric acid, 50g/L hydrogen peroxide, 10g/L zinc dichromate, 120g/L urea, 5g/L sodium dodecyl benzene sulfonate and the balance of water. And (3) uniformly mixing the substances to prepare a chemical milling solution.
Placing the chemical milling parts into aviation gasoline, soaking for 10-20 minutes to remove oil stains on the surfaces of the parts, then cleaning with warm water of 40-50 ℃ and drying, immersing the cleaned parts in the chemical milling solution of 65 ℃ until the size meets the requirement, taking out the parts, and cleaning with warm water of 40-50 ℃ to remove the residual chemical milling solution on the surfaces. The surface of the product after chemical milling has no defects of ridge beam, intergranular corrosion and the like, the chemical milling speed is 0.023mm/min, and the hydrogen content after chemical milling is increased by 3 ppm.
Example 6
The chemical milling solution comprises the following components: 125g/L of hydrofluoric acid, 480g/L of nitric acid, 250g/L of hydrogen peroxide, 5g/L of hexamethylenetetramine, 50g/L of urea, 5g/L of sodium dodecyl benzene sulfonate and the balance of water. And (3) uniformly mixing the substances to prepare a chemical milling solution.
And (2) placing the chemical milling parts into aviation gasoline, soaking for 10-20 minutes to remove oil stains on the surfaces of the parts, then cleaning with warm water of 40-50 ℃ and drying, immersing the cleaned parts in the chemical milling solution of 55 ℃ until the size meets the requirement, taking out the parts, and cleaning with warm water of 40-50 ℃ to remove the residual chemical milling solution on the surfaces. The surface of the product after chemical milling has no defects of pits, ridge beams, intergranular corrosion and the like, the chemical milling speed is 0.017mm/min, and the hydrogen content after chemical milling is increased by 9 ppm.
Example 7
The chemical milling solution comprises the following components: 180g/L of hydrofluoric acid, 600g/L of nitric acid, 150g/L of hydrogen peroxide, 3g/L of ammonium hexafluorophosphate, 100g/L of urea, 5g/L of sodium stearate, 50g/L of metal titanium powder and the balance of water. And (3) uniformly mixing the substances to prepare a chemical milling solution.
Placing the chemical milling parts into aviation gasoline, soaking for 10-20 minutes to remove oil stains on the surfaces of the parts, then cleaning with warm water of 40-50 ℃ and drying, immersing the cleaned parts in the chemical milling solution of 65 ℃ until the size meets the requirement, taking out the parts, and cleaning with warm water of 40-50 ℃ to remove the residual chemical milling solution on the surfaces. The surface of the product after chemical milling has no defects of pits, ridge beams, intergranular corrosion and the like, the chemical milling speed is 0.035mm/min, and the hydrogen content after chemical milling is increased by 4 ppm.
Example 8
The chemical milling solution comprises the following components: 220g/L hydrofluoric acid, 500g/L nitric acid, 280g/L hydrogen peroxide, 1.5g/L pyridine, 1.5g/L furfural, 100g/L urea, 5g/L sodium stearate, 25g/L Ti3Al intermetallic compound particles and the balance water. And (3) uniformly mixing the substances to prepare a chemical milling solution. Wherein, the components of the Ti3Al intermetallic compound are as follows (atomic ratio): ti-25Al-13Nb-1 Cr.
And (2) placing the chemical milling parts into aviation gasoline, soaking for 10-20 minutes to remove oil stains on the surfaces of the parts, then cleaning with warm water of 40-50 ℃ and drying, immersing the cleaned parts in the chemical milling solution of 45 ℃ until the size meets the requirement, taking out the parts, and cleaning with warm water of 40-50 ℃ to remove the residual chemical milling solution on the surfaces. The surface of the product after chemical milling has no defects of pits, ridge beams, intergranular corrosion and the like, the chemical milling speed is 0.035mm/min, and the hydrogen content after chemical milling is increased by 5 ppm.
The results of the examples show that the chemical milling solution formula and the chemical milling method provided by the invention can realize the chemical milling processing of titanium alloy or titanium-aluminum intermetallic compound materials. Has the advantages of low hydrogen absorption, high production efficiency, simple process, low cost and the like.
Claims (7)
1. The chemical milling solution of pure titanium, titanium alloy or titanium-aluminum intermetallic compound is characterized by comprising the following components: 20-350 g/L hydrofluoric acid, 150-750 g/L nitric acid, 50-550 g/L hydrogen peroxide, 0.5-20 g/L corrosion inhibitor, 5-200 g/L urea, 0.5-25 g/L surfactant, 0-180 g/L metal ions and the balance of water.
2. The chemical milling solution of pure titanium, titanium alloy or titanium-aluminum intermetallic compound according to claim 1 characterized in that the corrosion inhibitor is one or more than two of sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium metaphosphate, sodium polyphosphate, sodium dichromate, potassium dichromate, zinc dichromate, sodium chromate, potassium chromate, ammonium hexafluorophosphate, hexamethylenetetramine, benzoic acid, trihydroxybenzoic acid, thiourea, acridine, pyridine, furfural.
3. The chemical milling solution of pure titanium, titanium alloy or titanium-aluminum intermetallic compound according to claim 1 characterized in that the surfactant is one or more of sodium benzoate, linear alkyl benzene sulfonic acid, sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, sodium glycocholate, dodecyl benzene sulfonic acid, sodium dodecyl benzene sulfonate, stearic acid, sodium stearate, alkylolamides, fatty alcohol polyoxyethylene ethers, alkylphenol ethoxylates.
4. A chemical milling solution of pure titanium, titanium alloy or titanium-aluminium intermetallic compound according to claim 1 characterized in that the metal ions are titanium ions and/or aluminium ions, added in the form of powder or particles of metal, alloy or intermetallic compound, respectively.
5. Use of a chemical milling solution using pure titanium, titanium alloy or titanium-aluminium intermetallic compound according to claim 1, characterized by the following steps:
(1) removing dust and oil stains on the surface of a part needing chemical milling;
(2) immersing the cleaned parts in the chemical milling solution, carrying out chemical milling processing at 35-75 ℃, taking out the parts immediately after reaching the chemical milling depth, and cleaning with warm water at 40-50 ℃ to remove the residual chemical milling solution on the surface.
6. The use of the chemical milling solution of pure titanium, titanium alloy or titanium-aluminum intermetallic compound according to claim 5 characterized in that in step (1), the dust on the surface of the parts is washed off with clean water, the greasy dirt on the surface is washed off with ethanol, acetone or aviation gasoline, and the parts are cleaned with clean water and dried.
7. The use of the chemical milling solution of pure titanium, titanium alloy or titanium-aluminum intermetallic compound according to claim 5 characterized in that in step (2) the chemical milling rate is 0.01-0.035 mm/min.
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| US20160340572A1 (en) * | 2013-12-11 | 2016-11-24 | Halliburton Energy Services, Inc. | Hydrofluoric acid acidizing composition compatible with sensitive metallurgical grades |
| CN109594076A (en) * | 2019-01-17 | 2019-04-09 | 模德模具(苏州工业园区)有限公司 | One kind freezes liquid medicine |
| CN113445053A (en) * | 2021-06-17 | 2021-09-28 | 上海大学 | Compound corrosion inhibitor of Mg-Al series alloy and preparation method and application thereof |
| CN115449302A (en) * | 2022-09-20 | 2022-12-09 | 江西鑫铂瑞科技有限公司 | Use method of novel polishing solution for electrolytic copper foil cathode titanium roller |
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| CN113445053A (en) * | 2021-06-17 | 2021-09-28 | 上海大学 | Compound corrosion inhibitor of Mg-Al series alloy and preparation method and application thereof |
| CN115449302A (en) * | 2022-09-20 | 2022-12-09 | 江西鑫铂瑞科技有限公司 | Use method of novel polishing solution for electrolytic copper foil cathode titanium roller |
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