CN118028800A - High-temperature-resistant, color-changing and corrosion-resistant treatment method for stainless steel workpiece - Google Patents
High-temperature-resistant, color-changing and corrosion-resistant treatment method for stainless steel workpiece Download PDFInfo
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 146
- 239000010935 stainless steel Substances 0.000 title claims abstract description 145
- 238000011282 treatment Methods 0.000 title claims abstract description 86
- 238000005260 corrosion Methods 0.000 title claims abstract description 52
- 230000007797 corrosion Effects 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 96
- 239000002253 acid Substances 0.000 claims abstract description 53
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000002161 passivation Methods 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- 238000002845 discoloration Methods 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- -1 fluorine ions Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000010963 304 stainless steel Substances 0.000 claims description 4
- 239000010965 430 stainless steel Substances 0.000 claims description 4
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910000619 316 stainless steel Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 38
- 239000012028 Fenton's reagent Substances 0.000 abstract description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 21
- 239000011651 chromium Substances 0.000 abstract description 21
- 229910052804 chromium Inorganic materials 0.000 abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052742 iron Inorganic materials 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 7
- 238000004381 surface treatment Methods 0.000 abstract description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001035 drying Methods 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000002791 soaking Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000010306 acid treatment Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 9
- 235000013024 sodium fluoride Nutrition 0.000 description 9
- 239000011775 sodium fluoride Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000009996 mechanical pre-treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 238000001978 electrochemical passivation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a treatment method for stainless steel workpiece with high temperature resistance, color change and corrosion resistance, and relates to the technical field of stainless steel surface treatment. According to the high-temperature-resistant, color-changing and corrosion-resistant treatment method for the stainless steel workpiece, the oxide film layer is formed on the surface of the stainless steel workpiece through oxidation baking treatment, the formed oxide film layer is removed through acid solution, iron and chromium elements on the surface of the stainless steel can be further separated, finally, fenton reagent is used for passivation, so that a chromium-rich or chromium-rich nickel system is formed on the surface of the stainless steel workpiece, the high-temperature-resistant capability of the stainless steel workpiece is improved, the chlorine ion corrosion-resistant capability of the stainless steel workpiece is improved, the effect of effectively improving the high-temperature-resistant, color-changing and chlorine ion corrosion-resistant effects is achieved, and the stainless steel workpiece product has the advantages of no color-changing behavior and salt corrosion resistance under the use condition of 350-400 ℃.
Description
Technical Field
The invention relates to the technical field of stainless steel surface treatment, in particular to a treatment method for stainless steel workpieces with high temperature resistance, color change and corrosion resistance.
Background
In the cooker industry, austenitic stainless steel is favored by corrosion resistance, high strength, hardness, wear resistance and no reaction with food, and in addition, ferrite stainless steel also has magnetism conductivity, can be used as an induction cooker contact material, and has a large number of applications in the cooker industry. However, when the temperature exceeds 200 ℃ in the cooking process of the stainless steel products, the stainless steel starts to turn yellow, and the higher the temperature is, the more serious the turn yellow becomes. However, the cooker is a common practice with a usage temperature exceeding 200 ℃, and yellowing means a defect affecting consumer usage public praise.
To solve the problem of high temperature discoloration of stainless steel, patent CN105543937B proposes a solution to electrolytic passivation, which is essentially the electrochemical polishing of stainless steel in a common phosphoric acid system. When stainless steel is corroded strongly during electrochemical polishing, the corrosion speed of each alloy element is different, iron is corroded more quickly, and chromium and nickel elements are relaxed greatly. The surface of the stainless steel subjected to electrolytic polishing is provided with an iron-poor chromium-rich nickel layer, so that the stainless steel has certain high-temperature discoloration resistance. This resistance to high temperature discoloration is approximately 280-300 ℃. However, the method has limited capability of improving high-temperature discoloration resistance, needs to change the surface treatment state of stainless steel, uses concentrated phosphoric acid to generate heavy metal ions such as chromium and nickel, has high cost and large pollution, and is more limited in implementation.
Patent CN 108359929B proposes a method of baking oxidation + pickling oxide film at high temperature, which realizes an iron-lean chromium-rich nickel layer by oxidizing iron element in advance and then pickling to remove the oxide film. The method has high baking temperature of 420-500 deg.C, and high baking cost. The baking at the temperature can not completely separate iron elements, austenite tissues can be destroyed on the surface layer of the stainless steel after pickling and removing iron, and the actual color-changing temperature can be 60-100 ℃ lower than the baking temperature. That is to say that the actual discoloration temperature of the baking at 420-500 ℃ is in the range of 350-400 ℃. In addition, microscopic cavities formed by the destruction of metallographic structures such as austenite and the like caused by iron precipitation can greatly reduce the corrosion resistance of stainless steel, and particularly, when in a neutral salt spray test and a boiled brine test, massive rust spots are easy to appear, and the stainless steel is more sensitive to chloride ions than untreated stainless steel.
Disclosure of Invention
The invention aims to solve the technical problem of improving the anti-discoloration performance of a stainless steel material at high temperature and the sensitivity of chloride ions after treatment, and provides a treatment method for resisting high-temperature discoloration of a stainless steel workpiece.
In order to solve the problems, the invention provides the following technical scheme:
The invention provides a treatment method for stainless steel workpieces with high temperature resistance, color change and corrosion resistance, which comprises the following steps:
S1, carrying out oxidation baking treatment on a stainless steel workpiece under an aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 350-400 ℃;
S2, chemically treating the baked stainless steel workpiece with an acid solution to remove an oxide film on the surface and performing selective weak corrosion;
s3, passivating the stainless steel workpiece by using Fenton solution to obtain a stainless steel workpiece resistant to high-temperature discoloration;
wherein the acid solution is a mixed solution of sulfuric acid solution, fluorine-containing ion solution and 5-sulfosalicylic acid solution.
In order to improve the corrosion efficiency of the surface oxide film, the acid solution should be corroded by using a strong acid solution, and the sulfuric acid solution is most suitable for: hydrochloric acid contains chloride ions and has strong corrosiveness to stainless steel; nitric acid is an oxidizing acid and is not suitable for removing oxides from the stainless steel surface.
In the present invention, the fluoride ion-providing agent of the acid solution includes at least one of sodium fluoride, potassium fluoride, ammonium fluoride, sodium hydrogen fluoride, potassium hydrogen fluoride, ammonium hydrogen fluoride, and hydrofluoric acid. In the embodiment of the invention, the fluoride ion solution is sodium fluoride to provide fluoride ions.
The high-temperature discoloration of stainless steel is essentially understood to be the result of the oxidation of the iron element on the surface of stainless steel at high temperature, and the more the iron element on the surface of stainless steel, the more pronounced the high-temperature discoloration, and therefore, any method for reducing the iron element on the surface of stainless steel is effective against the high-temperature discoloration. In the treatment method of the invention, when the stainless steel workpiece is baked at high temperature, the iron element in the stainless steel alloy is separated from the chromium-nickel element due to oxidation.
According to the invention, the stainless steel workpiece is oxidized and baked to generate an iron-rich chromium-nickel-poor oxide film system, then the oxide film system is subjected to chemical etching by an acid solution, so that oxides on the surface of the stainless steel workpiece can be effectively removed, and further, the iron element is selectively corroded, thereby forming a chromium-rich or chromium-nickel-rich element system on the surface of the stainless steel workpiece, and finally, the surface of the stainless steel workpiece is subjected to passivation treatment by using a Fenton reagent, so that a continuous chromium-rich or chromium-nickel-rich system can be formed on the surface of the stainless steel workpiece, and the high-temperature resistance and the chloride ion corrosion resistance of the stainless steel workpiece are greatly improved.
Preferably, the temperature of the baking treatment is 360-400 ℃, and more preferably, the temperature of the baking treatment is 380-390 ℃. The baking treatment in the temperature range can lead the surface of the stainless steel workpiece to be easy to form an iron-containing oxide film layer, and the thickness of the oxide film layer is proper. The oxide film layer is a system which is rich in iron and poor in chromium and nickel by oxidizing iron into ferric oxide, can be effectively removed after acid treatment, so that the surface of a stainless steel workpiece is a chromium-rich or chromium-rich nickel element system, and can recover and improve the chloride ion corrosion resistance of the stainless steel workpiece after further Fenton reagent passivation treatment.
Further, the acid solution is a mixed solution of sulfuric acid solution, fluorine-containing ion solution and 5-sulfosalicylic acid solution.
The acid solution contains hydrogen ions and fluorine ions, and the hydrogen ions provided by the sulfuric acid have the effects of dissolving an oxide film layer on the surface of the stainless steel and continuously corroding Fe element; the fluoride ion has the capability of damaging the stainless steel passivation film and assists the hydrogen ion to further corrode the stainless steel; under acidic conditions, 5-sulfosalicylic acid can sequester iron ions, making corrosion more targeted to elemental iron. The invention adopts the specially prepared acid solution to react with ferric oxide and further selectively corrode Fe element, thereby achieving the effect of removing the oxide in the oxide film layer, recovering the natural color of the stainless steel workpiece and ensuring the stainless steel surface to be basically undamaged; meanwhile, the acid solution can further weakly corrode the stainless steel, so that the surface of the stainless steel workpiece can reach a chromium-rich or chromium-nickel-rich system, and better high-temperature anti-discoloration capability is realized. The basic principle of the chemical etching treatment of the surface by adopting the acid solution is as follows:
Fe 2O3+6H+→2Fe3++3H2 O (oxide film removal);
Fe-Cr-Ni+2H2 +→Cr-Ni+Fe2++H2 (austenite, e.g., 304);
Fe-Cr+2H +→Cr+Fe2++H2 (ferrite, e.g., 430).
Further, in the acid solution, the concentration of the sulfuric acid solution is 50-200g/L, the concentration of the fluorine ions is 5-10g/L, and the concentration of the 5-sulfosalicylic acid solution is 10-30g/L. .
Further, the Fenton solution consists of 30-100g/L hydrogen peroxide and 10-50g/L ferrous sulfate solution.
In the treatment method, the workpiece subjected to the chemical treatment by the acid solution is further subjected to passivation treatment by a Fenton (Fenton) reagent. The Fenton reagent is a mixed solution of hydrogen peroxide (H 2O2) and ferrous ions, has strong oxidizing property, contains a large amount of hydroxyl radicals, is a substance with strong oxidizing property, can enable stainless steel separated by selective iron and chromium elements to discontinuously passivate the surface and forcedly enter an anode passivation area, so that the passivation film on the surface of the stainless steel is recovered to have the corrosion resistance to chloride ions.
Further, the pH value of the Fenton solution is 2.0-3.0, and the pH value of the Fenton reagent is controlled by adding sulfuric acid, so that the Fenton reagent under the pH value range can generate a large amount of hydroxyl free radicals. The basic principle of passivating a surface by using Fenton's reagent is as follows:
Fe2++H2O2→Fe3++(OH)-+OH·。
further, the Fenton solution has an ORP value > 1000mV.
Further, the baking treatment in the step S1 is performed for a period of 5 minutes or more, preferably 5 to 10 minutes.
Further, the chemical treatment in the step S2 is carried out at a temperature of 30-50 ℃ for 2-5 minutes.
Further, the passivation treatment in step S3 is performed for 30 seconds or more, preferably 30 to 180 seconds.
Further, the material of the stainless steel workpiece comprises 304 stainless steel, 340L stainless steel, 430 stainless steel or 316 stainless steel.
In the above-described method for treating a stainless steel workpiece against discoloration, the stainless steel workpiece is preferably formed by processing a ferritic stainless steel material or an austenitic stainless steel material.
In the above-mentioned method for treating a stainless steel workpiece against discoloration, the stainless steel workpiece may be any of various products including a stainless steel plate or processed from a stainless steel material, and the specific form or product of the workpiece is not particularly limited, as long as the range is applicable in order to achieve the improvement of the high-temperature discoloration resistance and corrosion resistance of the stainless steel material.
As a further preference, the stainless steel workpiece is selected from stainless steel cookware.
Compared with the prior art, the invention has the following technical effects:
According to the high-temperature-resistant, color-changing and corrosion-resistant treatment method for the stainless steel workpiece, the oxide film layer is formed on the surface of the stainless steel workpiece through oxidation baking treatment, the formed oxide film layer is removed through acid solution, iron and chromium elements on the surface of the stainless steel can be further separated, finally, fenton reagent is used for passivation, so that a chromium-rich or chromium-rich nickel system is formed on the surface of the stainless steel workpiece, the high-temperature-resistant capability of the stainless steel workpiece is improved, the chlorine ion corrosion-resistant capability of the stainless steel workpiece is improved, the effect of effectively improving the high-temperature-resistant, color-changing and chlorine ion corrosion-resistant effects is achieved, and the stainless steel workpiece product has the advantages of no color-changing behavior and salt corrosion resistance under the use condition of 350-400 ℃.
Detailed Description
The technical solutions in the embodiments will be clearly and completely described below. It will be apparent that the embodiments described below are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of embodiments of the invention. As used in the specification of the embodiments of the invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The stainless steel workpiece adopted in the treatment method for resisting high temperature, color change and corrosion of the stainless steel workpiece can be formed by adopting a common machining or stamping mode to form the corresponding stainless steel workpiece, wherein the stainless steel workpiece can be formed by drawing, spinning, extrusion and the like, and the specific product of the stainless steel workpiece is not particularly limited, such as a stainless steel plate, a stainless steel oven and the like, and a stainless steel cooker such as a stainless steel pot, a stainless steel spoon and the like. The stainless steel workpiece may be made of various stainless steel materials, such as 304 stainless steel, 340L stainless steel, 430 stainless steel, 316 stainless steel, etc., without specific limitation.
Further, the method also comprises the step of carrying out certain mechanical pretreatment on the stainless steel workpiece subjected to the machining forming, wherein the treatment comprises mechanical polishing, wire drawing, sanding, rolling, polishing and the like. Conventional treatments such as degreasing and the like can also be included. The corresponding stainless steel workpieces in the following and corresponding examples and comparative examples can be formed by the pretreatment method.
The invention provides a treatment method for stainless steel workpiece with high temperature resistance, color change and corrosion resistance, which comprises the following steps:
s1, carrying out oxidation baking treatment on a stainless steel workpiece under an aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 350-400 ℃.
Placing the processed and formed stainless steel workpiece into a baking oven or a baking channel to perform oxidation baking treatment for a certain time under the aerobic condition; the surface oxide film generated after baking is an oxide system rich in iron and poor in chromium and nickel, and the oxide can be effectively removed during subsequent acid treatment, so that the surface of the stainless steel workpiece forms a chromium and nickel-rich or chromium-rich system.
The temperature of the oxidizing baking treatment of the embodiment of the invention is between 350 and 400 ℃. The baking time is up to the set temperature and is maintained for more than 5 minutes, and the baking time is usually 5-10 minutes.
S2, chemically treating the baked stainless steel workpiece with an acid solution to remove the oxide film on the surface, and performing selective weak corrosion.
The stainless steel workpiece subjected to the baking treatment is subjected to chemical etching treatment in an acid solution, so that oxides in the surface oxide film layer can be effectively removed, and iron elements in holes can be further selectively removed through corrosion.
The acid solution used in the examples of the present invention was formulated as follows:
Sulfuric acid (H + is provided) 50-200g/L;
sodium fluoride (providing F -) 5-10g/L;
10-30g/L of 5-sulfosalicylic acid.
When the acid treatment is carried out, the reaction speed can be accelerated by properly heating, and in the embodiment of the invention, the temperature range of the acid treatment is 20-50 ℃ and the reaction time is 2-5 minutes. After the treatment of the step, the stainless steel workpiece can recover the color before the treatment, a chromium-nickel-rich or chromium-rich system is formed on the surface, and the high-temperature color change resistance is further improved.
The concentration of the acid solution is related to the treatment time and the treatment temperature, and the higher the concentration is, the more corrosive the solution is, the higher the risk is, the higher the operation requirement is, and the over-corrosion is easily caused. Therefore, in practical production, the concentration of the acid solution should not be too high.
In other embodiments, potassium fluoride may also be used to provide fluoride ions.
S3, passivating the stainless steel workpiece by using Fenton solution to obtain the stainless steel workpiece resistant to high-temperature discoloration.
In the embodiment, after the acidification treatment, the workpiece is passivated by using a Fenton reagent solution, and damaged austenite and ferrite tissues in the workpiece are passivated again by using the high potential of hydroxyl free radicals in the Fenton reagent, so that the workpiece has good chloride ion corrosion resistance. The passivation treatment by using the Fenton reagent solution can be carried out at room temperature, and the reaction time is more than 30 seconds, preferably 30-180 seconds.
The Fenton reagent formulation described in this example is as follows:
30-100g/L hydrogen peroxide;
Ferrous sulfate 10-50g/L.
The pH value is 2.0-3.0, and the ORP value is more than 1000mV.
And finally, carrying out subsequent cleaning treatment on the stainless steel workpiece subjected to the passivation treatment, and drying to obtain a product capable of being packaged and delivered.
In order to further describe the technical scheme of the invention, the following stainless steel workpiece is specifically selected as a stainless steel cooker product for specific implementation and explanation. The main structure of the cooker is 304 stainless steel, the composite bottom is 430 stainless steel, the inner surface is sanded, the outer surface is mirror polished, and the composite bottom is sanded.
Example 1
Oxidizing and baking the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 350 ℃;
Immersing the baked stainless steel workpiece in an acid solution at 40 ℃ for 3 minutes, and performing chemical treatment to remove an oxide film on the surface and performing selective weak corrosion;
And (3) soaking the workpiece treated by the acid solution for 1 minute by using Fenton reagent solution, then cleaning by using deionized water, and drying.
The acid solution used in this example was a mixed solution of 100g/L sulfuric acid, 8g/L sodium fluoride, 20 g/L5-sulfosalicylic acid.
The Fenton reagent used in the embodiment is a mixed solution of 50g/L hydrogen peroxide and 30g/L ferrous sulfate, the pH value is 2.0, and the ORP value is more than 1000mV.
Example 2
Carrying out oxidation baking treatment on the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 380 ℃;
Immersing the baked stainless steel workpiece in an acid solution at 40 ℃ for 3 minutes, and performing chemical treatment to remove an oxide film on the surface and performing selective weak corrosion;
And (3) soaking the workpiece treated by the acid solution for 1 minute by using Fenton reagent solution, then cleaning by using deionized water, and drying.
The acid solution used in this example was a mixed solution of 100g/L sulfuric acid, 8g/L sodium fluoride, 20 g/L5-sulfosalicylic acid.
The Fenton reagent used in the embodiment is a mixed solution of 50g/L hydrogen peroxide and 30g/L ferrous sulfate, the pH value is 2.0, and the ORP value is more than 1000mV.
Example 3
Oxidizing and baking the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 400 ℃;
Immersing the baked stainless steel workpiece in an acid solution at 40 ℃ for 3 minutes, and performing chemical treatment to remove an oxide film on the surface and performing selective weak corrosion;
And (3) soaking the workpiece treated by the acid solution for 1 minute by using Fenton reagent solution, then cleaning by using deionized water, and drying.
The acid solution used in this example was a mixed solution of 100g/L sulfuric acid, 8g/L sodium fluoride, 20 g/L5-sulfosalicylic acid.
The Fenton reagent used in the embodiment is a mixed solution of 50g/L hydrogen peroxide and 30g/L ferrous sulfate, the pH value is 2.0, and the ORP value is more than 1000mV.
Example 4
Carrying out oxidation baking treatment on the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 380 ℃;
immersing the baked stainless steel workpiece in an acid solution at 30 ℃ for 3 minutes, and performing chemical treatment to remove an oxide film on the surface and performing selective weak corrosion;
And (3) soaking the workpiece treated by the acid solution for 1 minute by using Fenton reagent solution, then cleaning by using deionized water, and drying.
The acid solution used in this example was a mixed solution of 100g/L sulfuric acid, 8g/L sodium fluoride, 20 g/L5-sulfosalicylic acid.
The Fenton reagent used in the embodiment is a mixed solution of 50g/L hydrogen peroxide and 30g/L ferrous sulfate, the pH value is 2.0, and the ORP value is more than 1000mV.
Example 5
Carrying out oxidation baking treatment on the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 380 ℃;
soaking the baked stainless steel workpiece in 50 ℃ acid solution for 3 minutes, and performing chemical treatment to remove an oxide film on the surface and performing selective weak corrosion;
And (3) soaking the workpiece treated by the acid solution for 1 minute by using Fenton reagent solution, then cleaning by using deionized water, and drying.
The acid solution used in this example was a mixed solution of 100g/L sulfuric acid, 8g/L potassium fluoride, 20 g/L5-sulfosalicylic acid.
The Fenton reagent used in the embodiment is a mixed solution of 50g/L hydrogen peroxide and 30g/L ferrous sulfate, the pH value is 2.0, and the ORP value is more than 1000mV.
Example 6
Carrying out oxidation baking treatment on the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 380 ℃;
Immersing the baked stainless steel workpiece in an acid solution at 60 ℃ for 3 minutes, and performing chemical treatment to remove an oxide film on the surface and performing selective weak corrosion;
And (3) soaking the workpiece treated by the acid solution for 1 minute by using Fenton reagent solution, then cleaning by using deionized water, and drying.
The acid solution used in this example was a mixed solution of 100g/L sulfuric acid, 8g/L sodium fluoride, 20 g/L5-sulfosalicylic acid.
The Fenton reagent used in the embodiment is a mixed solution of 50g/L hydrogen peroxide and 30g/L ferrous sulfate, the pH value is 2.0, and the ORP value is more than 1000mV.
The workpiece obtained in this example is whitened, and there is a quality problem of overetching.
Comparative example 1
Carrying out oxidation baking treatment on the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 380 ℃;
And (3) soaking the baked stainless steel workpiece in an acid solution at 40 ℃ for 3 minutes, performing chemical treatment to remove an oxide film on the surface, performing selective weak corrosion, then cleaning with deionized water, and drying.
The acid solution used in this example was a mixed solution of 100g/L sulfuric acid, 8g/L sodium fluoride, 20 g/L5-sulfosalicylic acid.
Comparative example 2
Carrying out oxidation baking treatment on the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 380 ℃;
Immersing the baked stainless steel workpiece in an acid solution at 40 ℃ for 3 minutes, and performing chemical treatment to remove an oxide film on the surface and performing selective weak corrosion;
And (3) soaking the workpiece treated by the acid solution for 1 minute by using Fenton reagent solution, then cleaning by using deionized water, and drying.
The acid solution used in this comparative example was a 10wt% sulfuric acid solution.
The Fenton reagent used in the comparative example is a mixed solution of 50g/L hydrogen peroxide and 30g/L ferrous sulfate, the pH value is 2.0, and the ORP value is more than 1000mV.
Comparative example 3
Carrying out oxidation baking treatment on the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 380 ℃;
And (3) soaking the baked stainless steel workpiece in an acid solution at 40 ℃ for 3 minutes, performing chemical treatment to remove an oxide film on the surface, performing selective weak corrosion, then cleaning with deionized water, and drying.
The acid solution used in this comparative example was a 10wt% sulfuric acid solution.
Comparative example 4
Oxidizing and baking the stainless steel cooker under the aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 450 ℃;
And (3) soaking the baked stainless steel workpiece in an acid solution at 40 ℃ for 3 minutes, performing chemical treatment to remove an oxide film on the surface, performing selective weak corrosion, then cleaning with deionized water, and drying.
The acid solution used in this comparative example was a 10wt% sulfuric acid solution.
Comparative example 5
And (3) electrolyzing the stainless steel cooker in an electrolytic polishing solution consisting of 60% phosphoric acid, 10% sulfuric acid and 10% chromic anhydride by mass fraction for 5 minutes at 15V voltage and 10A/dm 2 current density, then washing with deionized water and drying. The stainless steel cooker of this comparative example was not baked.
Comparative example 6
Stainless steel cookware is not subjected to any baking treatment and chemical treatment after mechanical pretreatment.
The respective stainless steel cooker products obtained in the above examples and comparative examples were randomly selected to conduct the highest discoloration temperature test and the neutral salt spray test, and the results are shown in the following table 1.
The detection method of the high-temperature-resistant color-changing temperature specifically comprises the following steps: and adjusting the temperature of the oven to be measured, recording the temperature value, putting the workpiece into the oven to bake for 1 hour, taking out the average value of the b values recorded in the Lab value of the color difference meter, and comparing the average value of the b values recorded before putting into the oven. The difference between the front and rear b values is delta b, and delta b is less than 0.2, namely no change is caused. The highest unchanged temperature value is the high temperature resistance color-changing temperature. Wherein, L of the color difference meter is brightness difference, a is red-green color difference, and b is yellow-blue color difference. b-is blue and b+ is yellow. After the stainless steel exceeds the color changing point, the higher the temperature is, the larger the delta b value is, and after the temperature reaches the temperature changing point, the b value is increased by 0.4-0.5 when the temperature is increased by 10 ℃.
The neutral salt spray test is carried out for 24 hours according to a neutral salt spray test (NSS) specified in national standard GB/T10125-2021 artificial atmosphere corrosion test salt spray test. ( And (3) injection: for 24 hours, most stainless steel cookware has failed. )
Table 1 results of performance tests of examples and comparative examples
From the results of examples 1 to 3, it can be seen that the temperature change point and the baking temperature are substantially uniform and the higher the temperature of the baking treatment, the higher the discoloration temperature point under the same conditions of the chemical treatment (acid treatment and Fenton reagent treatment). While comparative examples 2-4 were treated with a different chemical treatment using a conventional acid solution, the discoloration temperature point was 60-80 c lower than the baking temperature.
In examples 2, 4 and 5, the temperatures of the baking treatments were the same, and the most important difference was that the temperatures of the acid treatments were different, and the temperatures of the acid treatments were higher and the final discoloration temperature points were also higher under the same acid solution and the same treatment time, so that the temperatures of the acid treatments (preferably 40 to 50 ℃) could be appropriately increased, but too high the temperatures of the acid treatments (for example, 60 ℃) could cause excessive corrosion of the work pieces, leading to whitening of the work pieces, and quality problems.
As can be seen from the comparison of example 2 and comparative examples 2 to 4, the acid treatment by immersing in the acid solution of the specific composition of the present invention can raise the discoloration temperature by 50 to 80 ℃. That is, the invention can realize the improvement of the color-changing temperature point by using lower baking temperature, and is more energy-saving. By comparing examples 1-3 with comparative examples 1-4, it was found that the treatment with Fenton's reagent solution has a remarkable repairing effect on the decrease in corrosion resistance to chloride ions caused by the destruction of metallographic structure after immersion in an acidic solution after baking, and is improved compared with the conventional stainless steel workpiece.
In the foregoing embodiments, the descriptions of the embodiments are focused on, and for those portions of one embodiment that are not described in detail, reference may be made to the related descriptions of other embodiments.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (9)
1. The treatment method for the stainless steel workpiece with high temperature resistance, color change and corrosion resistance is characterized by comprising the following steps:
S1, carrying out oxidation baking treatment on a stainless steel workpiece under an aerobic condition to form an oxide film on the surface, wherein the temperature of the baking treatment is 350-400 ℃;
S2, chemically treating the baked stainless steel workpiece with an acid solution to remove an oxide film on the surface and performing selective weak corrosion;
s3, passivating the stainless steel workpiece by using Fenton solution to obtain a stainless steel workpiece resistant to high-temperature discoloration;
wherein the acid solution is a mixed solution of sulfuric acid solution, fluorine-containing ion solution and 5-sulfosalicylic acid solution.
2. The method for treating a stainless steel workpiece with high temperature discoloration resistance and corrosion resistance according to claim 1, wherein the concentration of sulfuric acid solution in the acid solution is 50-200g/L, the concentration of fluorine ions is 5-10g/L, and the concentration of 5-sulfosalicylic acid solution is 10-30g/L.
3. The method for treating stainless steel workpieces with high temperature resistance, color change and corrosion resistance according to claim 1, wherein the Fenton solution consists of 30-100g/L hydrogen peroxide and 10-50g/L ferrous sulfate solution.
4. The method for treating a stainless steel workpiece with high temperature discoloration resistance and corrosion resistance according to claim 4, wherein the pH value of the Fenton solution is 2.0-3.0.
5. The method for treating a stainless steel workpiece with high temperature discoloration and corrosion resistance according to claim 4, wherein the Fenton solution has an ORP value of > 1000mV.
6. The method for treating a stainless steel workpiece with high temperature discoloration resistance and corrosion resistance according to claim 1, wherein the baking treatment in the step S1 is performed for 5 to 10 minutes.
7. The method for treating a stainless steel workpiece with high temperature discoloration resistance and corrosion resistance according to claim 1, wherein the chemical treatment in the step S2 is performed at a temperature of 30-50 ℃ for 2-5 minutes.
8. The method for treating a stainless steel workpiece with high temperature discoloration resistance and corrosion resistance according to claim 1, wherein the passivation treatment in the step S3 is performed for 30-180 seconds.
9. The method of treating a stainless steel workpiece to resist high temperature discoloration and corrosion according to claim 1, wherein the material of the stainless steel workpiece comprises 304 stainless steel, 340L stainless steel, 430 stainless steel, or 316 stainless steel.
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