CN115838954A - Surface treatment process suitable for gas diffuser of CVD (chemical vapor deposition) equipment - Google Patents
Surface treatment process suitable for gas diffuser of CVD (chemical vapor deposition) equipment Download PDFInfo
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- CN115838954A CN115838954A CN202211431706.4A CN202211431706A CN115838954A CN 115838954 A CN115838954 A CN 115838954A CN 202211431706 A CN202211431706 A CN 202211431706A CN 115838954 A CN115838954 A CN 115838954A
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004381 surface treatment Methods 0.000 title claims abstract description 33
- 238000005229 chemical vapour deposition Methods 0.000 title description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 108
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 104
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003814 drug Substances 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 239000000047 product Substances 0.000 claims description 42
- 238000005238 degreasing Methods 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 238000005237 degreasing agent Methods 0.000 claims description 25
- 239000013527 degreasing agent Substances 0.000 claims description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 20
- 238000012650 click reaction Methods 0.000 claims description 20
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- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000002390 rotary evaporation Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000007259 addition reaction Methods 0.000 claims description 12
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
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- 239000003208 petroleum Substances 0.000 claims description 8
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- 229910052719 titanium Inorganic materials 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 claims description 5
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
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- 230000001502 supplementing effect Effects 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims 2
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 18
- 239000011148 porous material Substances 0.000 abstract description 11
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 5
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- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000011975 tartaric acid Substances 0.000 abstract description 5
- 235000002906 tartaric acid Nutrition 0.000 abstract description 5
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- 238000000576 coating method Methods 0.000 abstract description 3
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- 238000012360 testing method Methods 0.000 description 26
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 238000005242 forging Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- 239000010407 anodic oxide Substances 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002048 anodisation reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
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- 230000009965 odorless effect Effects 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
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- 239000004328 sodium tetraborate Substances 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000724404 Homo sapiens Saccharopine dehydrogenase Proteins 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
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- SPZAGEJGELYZAM-UHFFFAOYSA-L copper sulfate hydrochloride Chemical group Cl.[Cu+2].[O-]S([O-])(=O)=O SPZAGEJGELYZAM-UHFFFAOYSA-L 0.000 description 1
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
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- Cleaning By Liquid Or Steam (AREA)
Abstract
The invention discloses a surface treatment process suitable for a gas diffuser of CVD equipment, belonging to the technical field of electrolytic or electrophoretic production process methods of coatings. The treatment process optimizes the oxidation liquid medicine in the anodic oxidation process, and adds a proper amount of tartaric acid, boric acid and citric acid as additives into the oxalic acid solution, thereby effectively reducing the dissolving capacity of the oxidation bath solution to the oxidation film during the oxidation period, improving the thickness of the oxidation film barrier layer and further improving the corrosion resistance of the oxidation film. In the surface treatment process, the invention adopts a segmented climbing low-voltage oxidation mode, so that the pore diameter of a porous layer of the oxide film is reduced, the generated oxide film is thinner, more compact and more uniform, and the content of impurity ions adsorbed in the film pores is reduced while the corrosion resistance of the oxide film is improved.
Description
Technical Field
The invention relates to the technical field of electrolytic or electrophoretic production process methods of coatings, in particular to a surface treatment process suitable for a gas diffuser of CVD equipment.
Background
The gas diffuser of the CVD equipment component is an aluminum flat plate structure, gas diffusion holes are uniformly distributed on the surface, and in the manufacturing industry of LTPS (low temperature polysilicon) and OLED (organic light emitting semiconductor), the anodic oxidation process of the CVD gas diffuser is to form a thin and compact oxide film on the surface of the gas diffuser in a specific solution by applying voltage.
Chinese patent CN113755925A discloses a method for surface modification of an aluminum forging by oxalic acid anodic oxidation, which comprises the following steps: (1) surface pretreatment of the aluminum forging: ultrasonically cleaning an aluminum forging piece by using an ethanol solution to remove oil, then polishing by using sand paper, cleaning the surface of the aluminum forging piece by using acetone and deionized water, and finally cleaning by using the ethanol solution in an ultrasonic cleaner and drying for later use; (2) anodizing of the aluminum forging: putting the aluminum forging into anodic oxidation liquid containing oxalic acid for anodic oxidation; washing the anodized aluminum forging with deionized water and drying the anodized aluminum forging with cold air to obtain an anodized film; (3) sealing the anodic oxide film: and (3) sealing and performing anti-corrosion treatment on the aluminum forging with the anodic oxide film formed on the surface in a solution containing dichromate and 1, 4-butynediol. The invention adopts constant voltage to carry out anodic oxidation, and the voltage is higher, and the technical problems that the pore diameter of a porous layer of an oxide film is larger and the generated oxide film is not compact and uniform enough exist after treatment.
The method is beneficial to reducing the pore diameter of an oxidation film by adopting a step boosting method, chinese patent CN113981500A provides an oxalic acid anodic oxidation process method of a hard aluminum alloy shell part, and the step boosting method is introduced to adjust and match the oxidation voltage, the oxidation time, the boosting speed and the frequency of an electrolytic cell, so that the three technical indexes of the appearance, the film thickness and the insulation resistance of the oxalic acid anodic oxidation film formed on the surface of the shell part reach the standard acceptance requirements, the qualification rate is high, the problem of part scrapping caused by film ablation and black points is thoroughly solved, the consistency of the insulation resistance of different parts of the shell part is ensured, and the quality of the oxalic acid anodic oxidation film of the shell part is greatly improved. According to the invention, the oxalic acid solution is adopted for anodic oxidation, so that the technical problems that the dissolving capacity of oxidation bath solution to an oxidation film is high during oxidation and the thickness of an oxidation film barrier layer is low exist; in addition, although the invention adopts a step boosting method, the voltage of anodic oxidation is high, and the degree of reduction of the pore diameter of the porous layer of the oxide film is limited.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the present invention provides a surface treatment process for a gas diffuser of a CVD apparatus, which can improve the corrosion resistance of an oxide film and prolong the service life.
An oxidizing agent solution comprising the following components in concentrations: 20-60 g/L oxalic acid, 10-20 g/L tartaric acid, 10-30 g/L boric acid, 5-10 g/L citric acid and the balance of water.
In the oxidation liquid medicine, a proper amount of tartaric acid, boric acid and citric acid are added into the oxalic acid solution as additives, so that the dissolving capacity of the oxidation tank liquid to an oxidation film during oxidation can be effectively reduced, the thickness of a barrier layer of the oxidation film is increased, and the corrosion resistance of the oxidation film is improved. In the surface treatment process, a segmented climbing low-voltage oxidation mode is adopted, the pore diameter of a porous layer of the oxide film is reduced, the generated oxide film is thinner, more compact and more uniform, and the content of impurity ions adsorbed in the film pores is reduced while the corrosion resistance of the oxide film is improved.
The invention discloses a preparation method of the oxidation liquid medicine in an anodic oxidation tank, which comprises the following steps:
step 1, cleaning an anodic oxidation tank at room temperature, adding 3/4 of pure water, measuring the pH value to be 7 +/-1, and measuring the conductivity to be less than or equal to 1uS/cm;
step 2, opening a temperature control system of the oxidation tank to control the temperature of the tank liquor to be 5-10 ℃;
step 3, adding 20-60 g/L oxalic acid, 10-20 g/L tartaric acid, 10-30 g/L boric acid and 5-10 g/L citric acid, starting to blow gas and stirring while adding, detecting the temperature in real time, and keeping the temperature between 5 and 10 ℃ all the time;
and 4, after the medicine is added, supplementing the working liquid level with pure water, continuously inflating and stirring until the medicine is completely dissolved in the bath solution, and finishing the preparation.
The invention provides a surface treatment process suitable for a gas diffuser of CVD equipment, which comprises the following steps:
s1, blocking and shielding a non-hoisting threaded hole of the gas diffuser by using an acid and alkali resistant rubber plug, installing a titanium alloy electrode screw in a hanging hole, starting hanging by using a corner titanium hanger, and hoisting the gas diffuser by using a crane after finishing hanging;
s2, transferring the gas diffuser to a rinsing bath, then degreasing the gas diffuser with degreasing liquid medicine, shaking the product back and forth to enable the degreasing liquid medicine to fully enter holes of the gas diffuser, lifting the gas diffuser out of the rinsing bath after the degreasing treatment is finished, and rinsing the surface of the product through high-pressure water with the pressure of more than or equal to 20MPa to ensure that no degreasing liquid medicine remains on the surface;
s3, alkali liquor is adopted to carry out alkali washing on the gas diffuser, and the alkali liquor needs to shake back and forth during the alkali washing so as to fully enter holes of the gas diffuser; after the alkaline cleaning, the gas diffuser is transferred and acid cleaning is carried out by adopting acid liquor, the acid liquor is required to shake back and forth during the acid cleaning so as to fully enter the hole of the gas diffuser, the gas diffuser is lifted out of a water washing tank after the acid cleaning, and the surface of the product is washed by high-pressure water with the pressure of more than or equal to 20MPa so as to ensure that no acid liquor is left on the surface;
s4, re-fastening the shielding rubber plugs and mounting and hanging electrode screws to ensure that the electrode screws are tightly connected with products during oxidation and prevent hanging points from being ablated due to poor conduction; confirming that the temperature and the concentration of the oxidation liquid medicine in the anodic oxidation tank are both in a control range, hanging the fastened gas diffuser into the anodic oxidation tank, and stirring to ensure that the temperature and the concentration of the oxidation liquid medicine are uniform during oxidation;
s5, setting a constant-voltage anodic oxidation program, starting a power supply, and turning off the power supply after oxidation is completed; after the gas diffuser is lifted out of the anodic oxidation tank, the surface of the product is washed by high-pressure water with the pressure of more than or equal to 20MPa, so that no oxidizing liquid medicine residue is left on the surface;
s6, hanging the gas diffuser into a pure water tank at normal temperature for washing for 3-5 min and a pure water tank at 40-50 ℃ for washing for 3-5 min in sequence, and shaking the gas diffuser back and forth to ensure that the holes are completely washed;
s7, hanging the gas diffuser out, and drying the gas diffuser by using clean oil-free compressed air; removing the angle titanium hanger and the electrode screw for hanging the gas diffuser, wiping and cleaning the threaded hole for hanging by using a cotton swab, and drying the threaded hole by using compressed air; and after the clamping hanger is disassembled, putting the gas diffuser into an oven for drying, and finishing the surface treatment of the gas diffuser.
Preferably, the degreasing liquid medicine in the step S2 is obtained by mixing an organic degreasing agent and water, and the concentration of the organic degreasing agent is 30-60 g/L.
Preferably, the temperature of the degreasing treatment in the step S2 is 45-55 ℃, and the treatment time is 5-10 min.
Preferably, the alkali solution in step S3 is a sodium hydroxide aqueous solution with the concentration of 20-40 g/L.
Preferably, the temperature of the alkali washing in the step S3 is 28-32 ℃, and the alkali washing time is 15-30S.
Preferably, the acid solution in step S3 is a nitric acid aqueous solution with a concentration of 150 to 250 g/L.
Preferably, the acid washing temperature in the step S3 is 25-35 ℃, and the acid washing time is 10-15 min.
Preferably, the anodization process in step S5 is as follows:
the residual oil stain on the surface of the base material can hinder the wetting with the oxidation liquid medicine, and the flatness and smoothness of the oxidation film and the combination degree of the oxidation film and the surface of the base material are influenced. If the surface of the gas diffuser is not completely degreased before the surface treatment, the oxide film is not uniformly adhered to the surface during the anodic oxidation. The greasy parts appear to have formed oxide film on the surface, but the distribution of the oxide film inside is uneven and the bonding with the matrix material is not firm, cracks or bubbles appear, and the quality of the oxide film is seriously reduced. Moreover, in the surface treatment process, oil stains can pollute the oxidation liquid medicine, reduce the surface treatment quality and cause a series of chain reactions.
In order to fully remove grease on the surface of the gas diffuser and avoid the adverse effect of the grease on the anodic oxidation treatment process, the invention adopts an organic degreasing agent to carry out degreasing treatment on the surface. The organic degreasing agent takes epoxy propanol, allyl alcohol glycidyl ether and potassium isopropoxide as raw materials, a polymer with a branched side chain is formed by polymerization, the polymer and 1-pentanethiol are subjected to click reaction to introduce a hydrophobic group, and then the polymer is subjected to addition reaction with methyl iodide after being subjected to subsequent reaction with 1-allyl imidazole to introduce a hydrophilic quaternary ammonium group. The organic degreasing agent has a three-dimensional structure, a branched side chain has rich functional groups and large intramolecular cavities, and the organic degreasing agent shows excellent solubility and low viscosity in an aqueous dispersion system. Degreasing liquid medicine prepared from the organic degreasing agent and water can reduce the oil-water interfacial tension of the oil stain of the base material, and the organic degreasing agent migrates to the interface and is arranged on the interface, so that the process of separating the oil stain from the surface of the base material is accelerated.
Preferably, the preparation method of the organic degreasing agent is as follows:
m1, uniformly mixing epoxy propanol, allyl alcohol glycidyl ether, potassium isopropoxide and tetrahydrofuran, and carrying out ring-opening polymerization reaction in an oxygen-free closed environment; after the ring-opening polymerization reaction is finished, adding hydrochloric acid to finish the reaction, stopping adding hydrochloric acid after no precipitate is generated, filtering and collecting filtrate, and performing rotary evaporation to remove tetrahydrofuran to obtain a ring-opening polymerization product for later use;
m2, taking the ring-opening polymerization product, 1-pentanethiol and tetrahydrofuran, mixing uniformly, adding a photoinitiator, and carrying out click reaction under the irradiation of ultraviolet light; removing tetrahydrofuran through rotary evaporation after the click reaction is finished to obtain a crude product, mixing the crude product with petroleum ether, filtering and collecting filtrate, and removing the petroleum ether from the filtrate through rotary evaporation to obtain a click reaction product for later use;
m3, mixing the click reaction product, 1-allyl imidazole, dibenzoyl peroxide and tetrahydrofuran uniformly, and carrying out polymerization reaction under an anaerobic condition; after the polymerization reaction is finished, removing tetrahydrofuran by rotary evaporation, washing with methanol, and drying to obtain a polymerization product for later use;
m4, taking the polymerization product and iodomethane, mixing uniformly, and then carrying out addition reaction under an oxygen-free closed condition; and after the addition reaction is finished, washing and drying the product by using ether to obtain the organic degreasing agent.
Specifically, the preparation method of the organic degreasing agent comprises the following steps of:
m1, uniformly mixing 2.95-3.85 parts of epoxy propanol, 4.55-5.90 parts of allyl alcohol glycidyl ether, 0.95-1.30 parts of potassium isopropoxide and 50-75 parts of tetrahydrofuran, and carrying out ring-opening polymerization reaction in an oxygen-free closed environment; after the ring-opening polymerization reaction is finished, adding hydrochloric acid to finish the reaction, stopping adding hydrochloric acid after no precipitate is generated, filtering and collecting filtrate, and performing rotary evaporation to remove tetrahydrofuran to obtain a ring-opening polymerization product for later use;
m2, taking 2.75-4.70 parts of the ring-opening polymerization product, 0.60-1.05 part of 1-pentanethiol and 40-60 parts of tetrahydrofuran, uniformly mixing, adding 0.05-0.10 part of benzoin dimethyl ether, and carrying out click reaction under the irradiation of ultraviolet light; removing tetrahydrofuran through rotary evaporation after the click reaction is finished to obtain a crude product, mixing the crude product with 35-50 parts of petroleum ether, filtering and collecting filtrate, and removing the petroleum ether through rotary evaporation to obtain a click reaction product for later use;
m3, taking 2.20-2.90 parts of the click reaction product, 0.60-1.10 parts of 1-allyl imidazole, 0.012-0.048 part of dibenzoyl peroxide and 40-60 parts of tetrahydrofuran, mixing uniformly, and carrying out polymerization reaction under the anaerobic condition; after the polymerization reaction is finished, removing tetrahydrofuran by rotary evaporation, washing with methanol at 0-4 ℃, and drying to obtain a polymerization product for later use;
m4, taking 2.65-3.40 parts of the polymerization product to be uniformly mixed with 30-60 parts of methyl iodide, and then carrying out addition reaction under an anaerobic closed condition; and after the addition reaction is finished, washing and drying the product by using ether to obtain the organic degreasing agent.
Preferably, the temperature of the ring-opening polymerization reaction in the step M1 is 60-75 ℃, and the reaction time is 6-18 h.
Preferably, the concentration of the hydrochloric acid in the step M1 is 0.5-1.0 mol/L.
Preferably, the wavelength of the ultraviolet light of the click reaction in the step M2 is 254-365 nm, and the reaction time is 0.5-2 h.
Preferably, the temperature of the polymerization reaction in the step M3 is 65-85 ℃, and the reaction time is 1-4 h.
Preferably, the temperature of the addition reaction in the step M4 is 40-50 ℃, and the reaction time is 12-48 h.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The introduction and the function of part of raw materials in the formula of the invention are as follows:
oxalic acid: organic matter of the chemical formula H 2 C 2 O 4 The crystal structure of the crystal is in two forms, namely alpha form (rhombohedral form) and beta form (monoclinic form), odorless, acid-tasted, soluble in water and ethanol, and insoluble in benzene and chloroform.
Tartaric acid: a carboxylic acid of formula C 4 H 6 O 6 White crystalline powder, soluble in water and ethanol, slightly soluble in ether.
Boric acid: an inorganic compound of the formula H 3 BO 3 It is white crystalline powder, has a greasy hand feeling and no odor.
Citric acid: citric acid with the molecular formula of C 6 H 8 O 7 It is an important organic acid, colorless crystal, odorless, strongly sour and easily soluble in water.
The invention has the beneficial effects that:
compared with the prior art, the proper amount of tartaric acid, boric acid and citric acid are added into the oxalic acid solution as additives, so that the dissolving capacity of the oxidation bath solution to the oxidation film during oxidation can be effectively reduced, the thickness of the oxidation film barrier layer is increased, and the corrosion resistance of the oxidation film is improved.
Compared with the prior art, the invention adopts a sectional climbing low-voltage oxidation mode, the pore diameter of the porous layer of the oxide film is reduced, the generated oxide film is thinner, more compact and more uniform, the corrosion resistance of the oxide film is improved, and the content of impurity ions adsorbed in the film pores is reduced.
The surface treatment process is adopted to treat the gas diffuser, the corrosion resistance of an oxide film is better, and the single use period is prolonged; by adopting the process, the thickness of the film layer can be reduced in the colleagues meeting the corrosion resistance requirement, and the thinner oxide film enables the porous structure of the oxide film to contain less impurity ions and water vapor, so that the convergence of the threshold voltage is better.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Allyl alcohol glycidyl ether, CAS No.: 106-92-3, available from Shanghai McClin Biotechnology, inc.
Example 1
A surface treatment process suitable for a gas diffuser of a CVD device comprises the following steps:
s1, blocking and shielding a non-hoisting threaded hole of the gas diffuser by using an acid and alkali resistant rubber plug, installing a titanium alloy electrode screw in a hanging hole, then starting to hang by using an angle titanium hanger, and hoisting the gas diffuser by using a crane after finishing hanging;
s2, transferring the gas diffuser to a water washing tank, degreasing the gas diffuser by using degreasing liquid medicine, wherein the degreasing temperature is 50 ℃, the degreasing time is 7.5min, the product needs to be shaken back and forth during the degreasing treatment to enable the degreasing liquid medicine to fully enter holes of the gas diffuser, the gas diffuser is lifted out of the water washing tank after the degreasing treatment is finished, and the surface of the product is washed by high-pressure water with the pressure of 20MPa to ensure that no degreasing liquid medicine residue exists on the surface;
s3, carrying out alkaline washing on the gas diffuser by adopting a sodium hydroxide aqueous solution with the concentration of 30g/L, wherein the temperature of the alkaline washing is 30 ℃, the time of the alkaline washing is 15S, and the alkaline washing needs to be shaken back and forth during the time to enable the alkaline solution to fully enter holes of the gas diffuser; after alkali washing, transferring the gas diffuser and carrying out acid washing by adopting nitric acid aqueous solution with the concentration of 200g/L, wherein the acid washing temperature is 30 ℃, the acid washing time is 10min, the gas diffuser needs to shake back and forth during the acid washing to enable acid liquor to fully enter holes of the gas diffuser, the gas diffuser is lifted out of a water washing tank after acid washing, and the surface of a product is washed by high-pressure water with the pressure of 20MPa to ensure that no acid liquor remains on the surface;
s4, re-fastening the shielding rubber plugs and mounting and hanging electrode screws to ensure that the electrode screws are tightly connected with products during oxidation and prevent hanging points from being ablated due to poor conduction; confirming that the temperature and the concentration of the oxidation liquid medicine in the anodic oxidation tank are both in a control range, hanging the fastened gas diffuser into the anodic oxidation tank, and stirring to ensure that the temperature and the concentration of the oxidation liquid medicine are uniform during oxidation;
s5, setting a constant-voltage anodic oxidation program, starting a power supply, wherein the anodic oxidation temperature is 15 ℃, and turning off the power supply after the oxidation is finished; after the gas diffuser is lifted out of the anodic oxidation tank, the surface of the product is washed by high-pressure water with the pressure of 20MPa, so that the surface of the product is ensured to have no residual oxidizing liquid medicine;
s6, hanging the gas diffuser into a pure water tank at normal temperature for washing for 4min, and hanging the gas diffuser into the pure water tank at 45 ℃ for washing for 4min, wherein the gas diffuser needs to be shaken back and forth during the washing to ensure that the holes are completely washed;
s7, hanging the gas diffuser out, and drying the gas diffuser by using clean oil-free compressed air; removing the angle titanium hanger and the electrode screw for hanging the gas diffuser, wiping and cleaning the threaded hole for hanging by using a cotton swab, and drying the threaded hole by using compressed air; and after the clamping hanger is disassembled, putting the gas diffuser into an oven for drying, and finishing the surface treatment of the gas diffuser.
The oxidation liquid medicine is prepared by the following method:
step 1, cleaning an anodic oxidation tank at room temperature, adding 3/4 of pure water, measuring the pH to be 7, and measuring the conductivity to be less than 1uS/cm;
step 2, opening a temperature control system of the oxidation tank to control the temperature of the tank liquor to be 10 ℃;
step 3, adding 40g/L oxalic acid, 15g/L tartaric acid, 20g/L boric acid and 7.5g/L citric acid, starting to blow gas and stirring while adding, detecting the temperature in real time, and keeping the temperature between 10 ℃ all the time;
and 4, after the medicine is added, supplementing the working liquid level with pure water, continuously inflating and stirring until the medicine is completely dissolved in the bath solution, and finishing the preparation.
The degreasing liquid medicine in the step S2 is obtained by mixing a commercial agent and water; the commercial agent is prepared by mixing sodium tetraborate, pentasodium triphosphate and water, wherein the mass fraction of the sodium tetraborate is 75%, and the mass fraction of the pentasodium triphosphate is 10%; the concentration of the commercial agent in the degreasing liquid medicine is 45g/L.
The anodization process in step S5 is as follows:
example 2
A surface treatment process suitable for a gas diffuser of a CVD device comprises the following steps:
s1, blocking and shielding a non-hoisting threaded hole of the gas diffuser by using an acid and alkali resistant rubber plug, installing a titanium alloy electrode screw in a hanging hole, starting hanging by using a corner titanium hanger, and hoisting the gas diffuser by using a crane after finishing hanging;
s2, transferring the gas diffuser to a water washing tank, degreasing the gas diffuser by using degreasing liquid medicine, wherein the degreasing temperature is 50 ℃, the degreasing time is 7.5min, the product needs to be shaken back and forth during the degreasing treatment to enable the degreasing liquid medicine to fully enter holes of the gas diffuser, the gas diffuser is lifted out of the water washing tank after the degreasing treatment is finished, and the surface of the product is washed by high-pressure water with the pressure of 20MPa to ensure that no degreasing liquid medicine residue exists on the surface;
s3, carrying out alkaline washing on the gas diffuser by adopting a sodium hydroxide aqueous solution with the concentration of 30g/L, wherein the temperature of the alkaline washing is 30 ℃, the time of the alkaline washing is 15S, and the alkaline washing needs to be shaken back and forth during the time to enable the alkaline solution to fully enter holes of the gas diffuser; after alkali washing, transferring the gas diffuser and carrying out acid washing by adopting nitric acid aqueous solution with the concentration of 200g/L, wherein the acid washing temperature is 30 ℃, the acid washing time is 10min, the gas diffuser needs to shake back and forth during the acid washing to enable acid liquor to fully enter holes of the gas diffuser, the gas diffuser is lifted out of a water washing tank after acid washing, and the surface of a product is washed by high-pressure water with the pressure of 20MPa to ensure that no acid liquor remains on the surface;
s4, re-fastening each shielding rubber plug and mounting and hanging an electrode screw to ensure that the electrode screw is tightly connected with a product during oxidation and prevent hanging points from being ablated due to poor conduction; confirming that the temperature and the concentration of the oxidation liquid medicine in the anodic oxidation tank are both in a control range, hanging the fastened gas diffuser into the anodic oxidation tank, and stirring to ensure that the temperature and the concentration of the oxidation liquid medicine are uniform during oxidation;
s5, setting a constant-voltage anodic oxidation program, starting a power supply, wherein the anodic oxidation temperature is 15 ℃, and turning off the power supply after the oxidation is finished; after the gas diffuser is lifted out of the anodic oxidation tank, the surface of the product is washed by high-pressure water with the pressure of 20MPa, so that no oxidizing liquid medicine residue is left on the surface;
s6, hanging the gas diffuser into a pure water tank at normal temperature for washing for 4min, and hanging the gas diffuser into the pure water tank at 45 ℃ for washing for 4min, wherein the gas diffuser needs to be shaken back and forth during the washing to ensure that the holes are completely washed;
s7, hanging the gas diffuser out, and drying the gas diffuser by using clean oil-free compressed air; removing the angle titanium hanger and the electrode screw for hanging the gas diffuser, wiping and cleaning the threaded hole for hanging by using a cotton swab, and drying the threaded hole by using compressed air; and after the clamping hanger is disassembled, putting the gas diffuser into an oven for drying, and finishing the surface treatment of the gas diffuser.
The oxidation liquid medicine is prepared by the following method:
step 1, cleaning an anodic oxidation tank at room temperature, adding 3/4 of pure water, measuring the pH to be 7, and measuring the conductivity to be less than 1uS/cm;
step 2, opening a temperature control system of the oxidation tank to control the temperature of the tank liquor to be 10 ℃;
step 3, adding 40g/L oxalic acid, 15g/L tartaric acid, 20g/L boric acid and 7.5g/L citric acid, starting to blow gas and stirring while adding, detecting the temperature in real time, and keeping the temperature between 10 ℃ all the time;
and 4, after the medicine is added, supplementing the working liquid level with pure water, continuously inflating and stirring until the medicine is completely dissolved in the bath solution, and finishing the preparation.
In the step S2, the degreasing liquid medicine is obtained by mixing an organic degreasing agent and water, wherein the concentration of the organic degreasing agent is 45g/L.
The anodization process in step S5 is as follows:
| serial number | Set voltage/V | Time to climb/min | Retention time/min |
| 1 | 3 | 2 | 2 |
| 2 | 6 | 2 | 2 |
| 3 | 9 | 2 | 2 |
| 4 | 12 | 3 | 3 |
| 5 | 15 | 3 | 3 |
| 6 | 18 | 3 | 3 |
| 7 | 21 | 3 | 5 |
| 8 | 24 | 3 | 5 |
The preparation method of the organic degreasing agent comprises the following steps:
m1, uniformly mixing 2.95kg of epoxy propanol, 4.55kg of allyl alcohol glycidyl ether, 0.95kg of potassium isopropoxide and 50kg of tetrahydrofuran, and carrying out ring-opening polymerization reaction in an oxygen-free closed environment, wherein the temperature of the ring-opening polymerization reaction is 65 ℃ and the reaction time is 12 hours; after the ring-opening polymerization reaction is finished, adding hydrochloric acid with the concentration of 1.0mol/L to finish the reaction, stopping adding the hydrochloric acid after no precipitate is generated, filtering and collecting filtrate, and removing tetrahydrofuran by rotary evaporation to obtain a ring-opening polymerization product for later use;
m2, taking 2.75kg of the ring-opening polymerization product, 0.60kg of 1-pentanethiol and 40kg of tetrahydrofuran, uniformly mixing, adding 0.05kg of benzoin dimethyl ether, and carrying out click reaction under the irradiation of ultraviolet light, wherein the wavelength of the ultraviolet light of the click reaction is 365nm, and the reaction time is 1h; removing tetrahydrofuran through rotary evaporation after the click reaction is finished to obtain a crude product, mixing the crude product with 35kg of petroleum ether, filtering and collecting filtrate, and removing the petroleum ether from the filtrate through rotary evaporation to obtain a click reaction product for later use;
m3, uniformly mixing 2.20kg of the click reaction product, 0.60kg of 1-allyl imidazole, 0.012kg of dibenzoyl peroxide and 40kg of tetrahydrofuran, and carrying out polymerization reaction at 75 ℃ for 2.5h under an oxygen-free condition; after the polymerization reaction is finished, removing tetrahydrofuran by rotary evaporation, washing with methanol at 0 ℃, and drying to obtain a polymerization product for later use;
m4, uniformly mixing another 2.65kg of the polymerization product with 30kg of methyl iodide, and then carrying out addition reaction under an oxygen-free closed condition, wherein the temperature of the addition reaction is 45 ℃ and the reaction time is 30 hours; and after the addition reaction is finished, washing and drying the product by using ether to obtain the organic degreasing agent.
Comparative example 1
The comparative example was substantially identical to the surface treatment process of example 1 except that the anodizing procedure was carried out for 50min using a constant voltage of 24V.
Comparative example 2
The comparative example is substantially identical to the surface treatment process of example 1 except that the formulation of the oxidizing chemical solution in the comparative example is an aqueous oxalic acid solution having a concentration of 82.5 g/L.
Test example 1
The corrosion resistance of the oxide film prepared by the surface treatment process is tested according to the national standard GB/T12967.3-2022 part 3 of the detection method of the aluminum and aluminum alloy anode oxide film and the organic polymer film: the specific method and steps in the salt spray test are carried out. The test method is a circulating accelerated salt spray test (CCT test), in particular to a CCT-AASS test. The test reagent is AASS test solution, spray test temperature of CCT-AASS test is 35 deg.C, 80cm 2 The average salt spray sedimentation rate of the horizontal area of the water-cooled salt spray is 1.5mL/h; in the drying test, the temperature in the oven is 60 ℃ and the relative humidity is 20 percent; in the damp-heat test, the temperature in the box is 50 ℃, and the relative humidity is 95%; the cycle was set to 4h spray test +2h dry test +2h damp heat test. According to the provisions of appendix B in the above standard, the corrosion of the anodized film after the test is observed and the corresponding protection grade is determined, when the protection grade is lower than grade 8, the evaluation is made according to the standard in the national standard GB T6461-2002 "rating of samples and test pieces after corrosion test of metals and other inorganic coatings on metal substrates". Adopt the bookThe corrosion resistance of the oxide film prepared by the surface treatment process of the present invention is represented by a protection grade, and the test results are shown in table 1.
Table 1:
after CCT-AASS test, the higher the protection level is, the stronger the corrosion resistance of the oxide film is.
Test example 2
The continuity of the oxide film prepared by the surface treatment process is tested according to the specific method and steps in the national standard GB/T8752-2006 copper sulfate method for the continuity test method of the aluminum and aluminum alloy anodic oxide film. The test reagent is copper sulfate-hydrochloric acid solution: 20g of crystalline copper sulfate (analytical grade) and 20mL of hydrochloric acid (. Rho.18g/mL) were taken and diluted to 1000mL with steamy water in a volumetric flask. Four drops of copper sulfate solution were dropped into the selected test site and left there for 5min, after which the solution was quickly wiped off. Inspecting the surface of the sample, and counting the number of black dots and red dots; the test temperature was 20 ℃. The continuity of the oxide film is represented by the number of black dots and red dots, and the test results are shown in table 2.
Table 2:
| name(s) | Number of black and red dots in the test area |
| Example 1 | 4 |
| Example 2 | 1 |
| Comparative example 3 | 9 |
| Comparative example 4 | 15 |
When the copper sulfate solution is dropped on the surface of the aluminum and aluminum alloy thin anodic oxide film with poor exposed matrix metal or oxide film, the copper is chemically deposited on the aluminum surface, and simultaneously, the naked eye or the low magnification magnifier is used for observation, so that gas is separated out from the part with exposed matrix metal. After the test, black spots or red spots can be observed at the discontinuous part of the oxide film, thereby judging the continuity of the aluminum and aluminum alloy thin anodic oxide film. The larger the number of black dots and red dots, the worse the continuity of the oxide film.
As can be seen from the test results in tables 1 and 2, example 2 has the best corrosion resistance and continuity. The reason for this may be that tartaric acid, boric acid and citric acid are added in proper amounts as additives to the oxalic acid solution in the oxidation solution, which can effectively reduce the dissolving capacity of the oxidation bath solution to the oxidation film during oxidation, increase the thickness of the oxidation film barrier layer and thus improve the corrosion resistance of the oxidation film. In the surface treatment process, a segmented climbing low-voltage oxidation mode is adopted, the pore diameter of a porous layer of the oxide film is reduced, the generated oxide film is thinner, more compact and more uniform, and the content of impurity ions adsorbed in the film pores is reduced while the corrosion resistance of the oxide film is improved.
In addition, example 2 uses an organic degreasing agent to degrease the substrate, the organic degreasing agent has a three-dimensional structure, the branched side chain has rich functional groups and large intramolecular cavities, and the organic degreasing agent shows excellent solubility and low viscosity in an aqueous dispersion system. The degreasing liquid medicine prepared from the organic degreasing agent and water can reduce the oil-water interfacial tension of the oil stain of the base material, the organic degreasing agent migrates to the interface and is arranged on the interface, the process that the oil stain is separated from the surface of the base material is accelerated, the problems that the oil stain blocks the infiltration with the oxidation liquid medicine, the flatness and smoothness of an oxidation film and the bonding degree with the surface of the base material are influenced are solved, and the pollution of the oil stain to the oxidation liquid medicine and the reduction of the surface treatment quality caused by the oil stain are prevented. So that the finished product has better corrosion resistance and continuity.
Claims (10)
1. A preparation method of an oxidation liquid medicine in an anodic oxidation tank is characterized by comprising the following steps:
step 1, cleaning an anodic oxidation tank at room temperature, adding 3/4 of pure water, measuring the pH value to be 7 +/-1, and measuring the conductivity to be less than or equal to 1uS/cm;
step 2, opening a temperature control system of the oxidation tank to control the temperature of the tank liquor to be 5-10 ℃;
step 3, adding 20-60 g/L oxalic acid, 10-20 g/L tartaric acid, 10-30 g/L boric acid and 5-10 g/L citric acid, starting to blow gas and stirring while adding, detecting the temperature in real time, and keeping the temperature between 5 and 10 ℃ all the time;
and 4, after the medicine is added, supplementing the working liquid level with pure water, continuously inflating and stirring until the medicine is completely dissolved in the tank liquor, and completing preparation.
2. An oxidizing agent solution, characterized in that: formulated by the method of claim 1.
3. A surface treatment process suitable for a gas diffuser of a CVD device, which is characterized in that the oxidation liquid medicine of claim 2 is used for carrying out anodic oxidation treatment, and the specific process steps are as follows:
s1, blocking and shielding a non-hoisting threaded hole of the gas diffuser by using an acid and alkali resistant rubber plug, installing a titanium alloy electrode screw in a hanging hole, starting hanging by using a corner titanium hanger, and hoisting the gas diffuser by using a crane after finishing hanging;
s2, transferring the gas diffuser to a rinsing bath, then degreasing the gas diffuser with degreasing liquid medicine, shaking the product back and forth to enable the degreasing liquid medicine to fully enter holes of the gas diffuser, lifting the gas diffuser out of the rinsing bath after the degreasing treatment is finished, and rinsing the surface of the product through high-pressure water with the pressure of more than or equal to 20MPa to ensure that no degreasing liquid medicine remains on the surface;
s3, alkali liquor is adopted to carry out alkali washing on the gas diffuser, and the alkali liquor needs to shake back and forth during the alkali washing so as to fully enter holes of the gas diffuser; after the alkaline cleaning, the gas diffuser is transferred and acid cleaning is carried out by adopting acid liquor, the acid liquor is required to shake back and forth during the process so as to fully enter holes of the gas diffuser, the gas diffuser is lifted out of a water washing tank after the acid cleaning, and the surface of the product is washed by high-pressure water with the pressure of more than or equal to 20MPa so as to ensure that no acid liquor is left on the surface;
s4, re-fastening the shielding rubber plugs and mounting and hanging electrode screws to ensure that the electrode screws are tightly connected with products during oxidation and prevent hanging points from being ablated due to poor conduction; confirming that the temperature and the concentration of the oxidation liquid medicine in the anodic oxidation tank are both in a control range, hanging the fastened gas diffuser into the anodic oxidation tank, and stirring to ensure that the temperature and the concentration of the oxidation liquid medicine are uniform during oxidation;
s5, setting a constant-voltage anodic oxidation program, starting a power supply, and turning off the power supply after oxidation is completed; after the gas diffuser is lifted out of the anodic oxidation tank, the surface of the product is washed by high-pressure water with the pressure of more than or equal to 20MPa, so that no oxidizing liquid medicine residue is left on the surface;
s6, hanging the gas diffuser into a pure water tank at normal temperature for washing for 3-5 min and a pure water tank at 40-50 ℃ for washing for 3-5 min in sequence, and shaking the gas diffuser back and forth to ensure that the holes are completely washed;
s7, hanging the gas diffuser out, and drying the gas diffuser by using clean oil-free compressed air; removing the angle titanium hanger and the electrode screw for hanging the gas diffuser, wiping and cleaning the threaded hole for hanging by using a cotton swab, and drying the threaded hole by using compressed air; and after the clamping hanger is disassembled, putting the gas diffuser into an oven for drying, and finishing the surface treatment of the gas diffuser.
4. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 3, wherein: in the step S2, the degreasing liquid medicine is obtained by mixing an organic degreasing agent with water, wherein the concentration of the organic degreasing agent is 30-60 g/L; the temperature of the degreasing treatment is 45-55 ℃, and the treatment time is 5-10 min.
5. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 3, wherein: the alkali liquor in the step S3 is a sodium hydroxide aqueous solution with the concentration of 20-40 g/L, the alkali washing temperature is 28-32 ℃, and the alkali washing time is 15-30S; the acid solution is nitric acid aqueous solution with the concentration of 150-250 g/L, the pickling temperature is 25-35 ℃, and the pickling time is 10-15 min.
6. The surface treatment process for the gas diffuser of the CVD apparatus according to claim 3, wherein the organic degreasing agent is prepared by the following steps in parts by weight:
m1, uniformly mixing 2.95-3.85 parts of epoxy propanol, 4.55-5.90 parts of allyl alcohol glycidyl ether, 0.95-1.30 parts of potassium isopropoxide and 50-75 parts of tetrahydrofuran, and carrying out ring-opening polymerization reaction in an oxygen-free closed environment; after the ring-opening polymerization reaction is finished, adding hydrochloric acid to finish the reaction, stopping adding hydrochloric acid after no precipitate is generated, filtering and collecting filtrate, and performing rotary evaporation to remove tetrahydrofuran to obtain a ring-opening polymerization product for later use;
m2, taking 2.75-4.70 parts of the ring-opening polymerization product, 0.60-1.05 parts of 1-pentanethiol and 40-60 parts of tetrahydrofuran, uniformly mixing, adding 0.05-0.10 part of benzoin dimethyl ether, and carrying out click reaction under the irradiation of ultraviolet light; removing tetrahydrofuran through rotary evaporation after the click reaction is finished to obtain a crude product, mixing the crude product with 35-50 parts of petroleum ether, filtering and collecting filtrate, and removing the petroleum ether through rotary evaporation to obtain a click reaction product for later use;
m3, taking 2.20-2.90 parts of the click reaction product, 0.60-1.10 parts of 1-allyl imidazole, 0.012-0.048 part of dibenzoyl peroxide and 40-60 parts of tetrahydrofuran, mixing uniformly, and carrying out polymerization reaction under the anaerobic condition; after the polymerization reaction is finished, removing tetrahydrofuran by rotary evaporation, washing with methanol at 0-4 ℃, and drying to obtain a polymerization product for later use;
m4, taking 2.65-3.40 parts of the polymerization product to be uniformly mixed with 30-60 parts of methyl iodide, and then carrying out addition reaction under an anaerobic closed condition; and after the addition reaction is finished, washing and drying the product by using ether to obtain the organic degreasing agent.
7. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 6, wherein: the temperature of the ring-opening polymerization reaction in the step M1 is 60-75 ℃, and the reaction time is 6-18 h.
8. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 6, wherein: the wavelength of the ultraviolet light of the click reaction in the step M2 is 254-365 nm, and the reaction time is 0.5-2 h.
9. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 6, wherein: the temperature of the polymerization reaction in the step M3 is 65-85 ℃, and the reaction time is 1-4 h.
10. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 6, wherein: the temperature of the addition reaction in the step M4 is 40-50 ℃, and the reaction time is 12-48 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2390588C1 (en) * | 2008-12-25 | 2010-05-27 | Открытое акционерное общество "Всероссийский институт легких сплавов" (ОАО "ВИЛС") | Procedure for hard anodising items out of aluminium alloys |
| CN107604342A (en) * | 2016-07-12 | 2018-01-19 | Abm股份有限公司 | Its manufacture method of hardware and the process chamber with hardware |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2390588C1 (en) * | 2008-12-25 | 2010-05-27 | Открытое акционерное общество "Всероссийский институт легких сплавов" (ОАО "ВИЛС") | Procedure for hard anodising items out of aluminium alloys |
| CN107604342A (en) * | 2016-07-12 | 2018-01-19 | Abm股份有限公司 | Its manufacture method of hardware and the process chamber with hardware |
Non-Patent Citations (2)
| Title |
|---|
| 何潘亮: "四酸体系铝合金瓷质氧化工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 022 - 37 * |
| 钱苗根: "材料表面技术及其应用手册", 机械工业出版社, pages: 230 * |
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