CN117758246A - Corrosion-resistant treatment method for steel material, corrosion-resistant steel material and phosphating solution - Google Patents
Corrosion-resistant treatment method for steel material, corrosion-resistant steel material and phosphating solution Download PDFInfo
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- CN117758246A CN117758246A CN202211139347.5A CN202211139347A CN117758246A CN 117758246 A CN117758246 A CN 117758246A CN 202211139347 A CN202211139347 A CN 202211139347A CN 117758246 A CN117758246 A CN 117758246A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 155
- 239000010959 steel Substances 0.000 title claims abstract description 155
- 238000005260 corrosion Methods 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000007797 corrosion Effects 0.000 title claims abstract description 41
- 239000010935 stainless steel Substances 0.000 title claims abstract description 11
- 238000005536 corrosion prevention Methods 0.000 claims abstract description 11
- 239000002981 blocking agent Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 65
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 21
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 20
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 12
- 229910000746 Structural steel Inorganic materials 0.000 claims description 11
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 10
- 229960004889 salicylic acid Drugs 0.000 claims description 10
- 235000010288 sodium nitrite Nutrition 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000005237 degreasing agent Methods 0.000 claims description 9
- 239000013527 degreasing agent Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000002480 mineral oil Substances 0.000 claims description 7
- 235000010446 mineral oil Nutrition 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010865 sewage Substances 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 description 17
- 239000010452 phosphate Substances 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 16
- 230000007935 neutral effect Effects 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000007921 spray Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The embodiment of the application provides a corrosion-resistant treatment method for steel, a corrosion-resistant steel and phosphating solution. The method for corrosion-resistant treatment of steel material comprises: providing steel and phosphating solution, carrying out phosphating treatment on the steel by adopting the phosphating solution, forming a phosphating film on the surface of the steel, wherein the phosphating film comprises a plurality of grains, and micropores are formed between adjacent grains; providing a blocking agent, and applying the blocking agent on the surface of the phosphating film so that the blocking agent enters micropores of the phosphating film. After the steel is subjected to corrosion prevention treatment by adopting the corrosion prevention treatment method of the steel, the corrosion resistance of the steel can be obviously improved, hexavalent chromium ions are not generated in the corrosion prevention treatment process of the steel, the sewage treatment cost is low, and hexavalent chromium ions are not remained on the surface of the treated steel.
Description
Technical Field
The application relates to the technical field of metal surface treatment, in particular to a corrosion-resistant treatment method for steel, a corrosion-resistant steel and phosphating solution.
Background
The ultra-high strength structural steel is a type of alloy steel used for manufacturing structural members bearing higher stress, the yield strength is generally more than 1180MPa, the tensile strength is more than 1380MPa, and the alloy steel has enough toughness and higher specific strength and yield ratio. The ultra-high strength structural steel has poor corrosion resistance due to the extremely low or no chromium content in the ultra-high strength structural steel.
At present, the ultra-high strength structural steel is generally subjected to corrosion prevention treatment by adopting a chromic acid passivation treatment method, however, hexavalent chromium ions are generated in the chromic acid passivation treatment process, are very environment-friendly and cannot be directly discharged, wastewater is required to be treated by adopting independent sewage treatment equipment, the treatment cost is high, and in addition, hexavalent chromium ions are easy to remain on the surface of the steel subjected to the passivation treatment, so that the method has a threat to human health.
Disclosure of Invention
The embodiment of the application provides a corrosion-resistant treatment method for steel, a corrosion-resistant steel and phosphating solution, after the corrosion-resistant treatment method for steel is adopted to carry out corrosion-resistant treatment on the steel, the corrosion resistance of the steel can be obviously improved, hexavalent chromium ions are not generated in the corrosion-resistant treatment process of the steel, the sewage treatment cost is low, and meanwhile hexavalent chromium ions cannot be remained on the surface of the treated steel.
In a first aspect, an embodiment of the present application provides a method for corrosion-resistant treatment of steel, including:
providing steel and phosphating solution, carrying out phosphating treatment on the steel by adopting the phosphating solution, and forming a phosphating film on the surface of the steel, wherein the phosphating film comprises a plurality of crystal grains, and micropores are formed between the adjacent crystal grains;
providing a blocking agent, and applying the blocking agent on the surface of the phosphating film so that the blocking agent enters micropores of the phosphating film.
In a second aspect, embodiments of the present application provide a corrosion-resistant steel having a surface with a phosphate film comprising a plurality of grains, wherein micropores are formed between adjacent ones of the grains, and wherein a sealant is contained in the micropores.
In a third aspect, embodiments of the present application provide a phosphating solution, including, in parts by weight: 31-39 parts of manganese nitrate, 18-22 parts of phosphoric acid, 8-12 parts of manganese dihydrogen phosphate, 7-13 parts of nickel nitrate, 6-8 parts of citric acid, 5-7 parts of salicylic acid, 4-6 parts of ethylenediamine tetraacetic acid, 4-6 parts of sodium nitrite, 1.5-2.5 parts of nitrous acid and 150-250 parts of water.
According to the anti-corrosion treatment method for the steel, the phosphating solution is adopted to carry out phosphating treatment on the steel, a phosphating film is formed on the surface of the steel, and then a sealing agent is applied to the surface of the phosphating film, so that the sealing agent enters micropores of the phosphating film, the phosphating film can be utilized to play an anti-corrosion effect, and the sealing agent can be utilized to fill the micropores in the phosphating film, so that the anti-corrosion effect of the phosphating film is further improved, and the corrosion resistance of the steel is further improved; after the steel is treated by adopting the anti-corrosion treatment method of the steel, the obtained anti-corrosion steel can be subjected to neutral salt spray test for more than 60 hours without corrosion, and meanwhile, the surface of the obtained anti-corrosion steel is black, so that the blackening treatment step after conventional passivation is omitted, and the process implementation cost is reduced; in addition, hexavalent chromium ions are not generated in the anti-corrosion treatment process of the steel, the sewage treatment cost is low, and hexavalent chromium ions are not remained on the surface of the treated steel.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below.
Fig. 1 is a flowchart of a method for corrosion protection treatment of steel provided in the example of the present application.
FIG. 2 is a photomicrograph of a phosphated film prepared in the examples of this application.
FIG. 3 is a photograph of the steel material subjected to the corrosion protection treatment in the example of the present application.
FIG. 4 is a photomicrograph of the surface of the steel material subjected to the anticorrosive treatment in example 1 of the present application.
FIG. 5 is a photograph showing a neutral salt spray test of the steel material subjected to the anticorrosive treatment in example 1 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
Referring to fig. 1, fig. 1 is a flowchart of a method for corrosion protection treatment of steel provided in an embodiment of the present application. The embodiment of the application provides an anti-corrosion treatment method for steel, which comprises the following steps:
s100, providing steel and phosphating solution, carrying out phosphating treatment on the steel by adopting the phosphating solution, forming a phosphating film on the surface of the steel, wherein the phosphating film comprises a plurality of crystal grains, and micropores are formed between the adjacent crystal grains.
Illustratively, the steel may be an ultra-high strength structural steel comprising, in parts by weight: 14 to 18 parts of nickel, 6 to 10 parts of cobalt, 2 to 4 parts of molybdenum, 2 to 4 parts of niobium, 0.3 to 0.7 part of vanadium, 0 to 0.2 part of carbon, 0 to 0.2 part of oxygen and 66 to 72 parts of iron.
Illustratively, in the ultra-high strength structural steel, the parts of nickel may be 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, etc., the parts of cobalt may be 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc., the parts of molybdenum may be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, etc., the parts of niobium may be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, etc., the parts of vanadium may be 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, etc., the parts of carbon may be 0 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, etc., the parts of oxygen may be 0 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, etc., and the parts of iron may be 66 parts, 67 parts, 68 parts, 69 parts, 70, 71 parts, 72 parts, etc. In some embodiments, the ultra-high strength structural steel may include 16 parts of nickel, 8 parts of cobalt, 3 parts of Mo, 3 parts of niobium, 0.5 parts of vanadium, 0.1 parts of carbon, 0.1 parts of oxygen, 69.3 parts of iron, in parts by weight.
Illustratively, the phosphating solution includes, in parts by weight: 31-39 parts of manganese nitrate, 18-22 parts of phosphoric acid, 8-12 parts of manganese dihydrogen phosphate, 7-13 parts of nickel nitrate, 6-8 parts of citric acid, 5-7 parts of salicylic acid, 4-6 parts of ethylenediamine tetraacetic acid, 4-6 parts of sodium nitrite, 1.5-2.5 parts of nitrous acid and 150-250 parts of water. It should be noted that in the phosphating solution provided in the embodiment of the present application, both manganese nitrate and manganese dihydrogen phosphate can play a role in providing manganese ions, and manganese dihydrogen phosphate can also play a role in providing phosphate radicals, where both manganese ions and phosphate radicals are used to form phosphating crystals; the nickel nitrate can react with acidic substances to generate nitric acid, and plays roles of an oxidant and an accelerator, so that the formation speed of a phosphating film is increased; the citric acid, the salicylic acid, the ethylenediamine tetraacetic acid (EDTA), the nitrous acid and the sodium nitrite can play a role in regulating and controlling the pH value of the phosphating solution together, and the pH value of the phosphating solution can be kept stable through the synergistic effect of the components, so that the speed of chemical reaction is kept stable.
Illustratively, the pH of the phosphating solution is 3.5 to 5.5, such as 3.5, 3.7, 4.0, 4.3, 4.5, 5.0, 5.2, 5.5, etc.
Illustratively, the parts of manganese nitrate (Mn (NO)) in the phosphating solution may be 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, etc., in parts by weight.
Illustratively, in the phosphating solution, phosphoric acid (H 3 PO 4 ) The parts of (a) may be 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, etc.
Illustratively, in the phosphating solution, manganese dihydrogen phosphate (Mn (H) 2 PO 4 ) 2 The portion of the markov salt) may be 8, 9, 10, 11, 12, etc.
Illustratively, nickel nitrate (Ni (NO 3 ) 2 ) The parts of (a) may be 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, etc.
Illustratively, the parts of citric acid in the phosphating solution may be 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, etc., in parts by weight.
Illustratively, the parts of salicylic acid in the phosphating solution may be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, etc., in parts by weight.
Illustratively, the parts of ethylenediamine tetraacetic acid (EDTA) in the phosphating solution may be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, etc., in parts by weight.
Illustratively, the parts of sodium nitrite (NaNO) in the phosphating solution may be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, etc., in parts by weight.
Illustratively, the parts of nitrous acid (HNO) in the phosphating solution may be 1.5 parts, 1.7 parts, 2 parts, 2.2 parts, 2.5 parts, etc., in parts by weight.
Illustratively, the parts of water in the phosphating solution may be 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, etc., in parts by weight.
In some embodiments, the phosphating solution comprises, in parts by weight: 35 parts of manganese nitrate, 20 parts of phosphoric acid, 10 parts of manganese dihydrogen phosphate, 10 parts of nickel nitrate, 7 parts of citric acid, 6 parts of salicylic acid, 5 parts of ethylenediamine tetraacetic acid, 5 parts of sodium nitrite, 2 parts of nitrous acid and 200 parts of water.
Specifically, the mechanism for generating the phosphating film by the reaction of the phosphating solution and the steel comprises:
1) Acid attack causes H on the surface of the steel + Concentration reduction;
Fe+H + →Fe 2+ +H 2
Fe 2+ +[O]→Fe 3+
2) A promoter (oxidant) accelerates the rate of the phosphorylation reaction;
[O]+[H]→[R]+H 2 O
Fe 3+ +[R]→Fe(R)
wherein, [ O ]]To promote the oxidation of (nitric acid), [ H ]]Comprises dihydrogen phosphate (H PO) - )，[R]Comprises Phosphate (PO) 4 3- ) The accelerator may be a catalyst which converts ferric ions (Fe 2+ ) Oxidation to ferrous ions (Fe) 3+ ) At the same time, can promote the conversion of dihydrogen phosphate (H PO-) into Phosphate (PO) 4 3- ) Accelerating the progress of the phosphating reaction.
3) Multistage ionization of phosphate radical, decomposition to produce H + Phosphate ions;
H 3 PO 4 →H 2 PO 4- +H + →HPO 4 2- +2H + →PO 4 3- →PO 4 3- +3H +
h of metal surface + The concentration drops sharply, resulting in the ionization balance of each stage of phosphate radical moving rightwardTo become phosphate ions.
4) Precipitating and crystallizing phosphate to obtain a phosphate film;
phosphate ions dissociated from the metal surface and metal ions (manganese ions, iron ions and the like) in the solution reach a solubility product constant to form phosphate precipitates; phosphate precipitation forms phosphating crystal nucleus together with water molecules, the crystal nucleus continues to grow to form phosphating crystal grains, and innumerable crystal grains are closely packed to form phosphating film.
Mn 2+ +Fe 3+ +PO 4 3- +H 2 O→Mn 2 Fe(PO 4 )2.4H 2 O
Mn 2+ +Fe 3+ +PO 4 3- +H 2 O→Mn 3 Fe(PO 4 )2.4H 2 O
As can be seen, mn 2 Fe(PO 4 )2.4H 2 O and Mn 3 Fe(PO 4 )2.4H 2 O is the main component of the phosphated crystal grain, and is used for removing Mn 2 Fe(PO 4 )2.4H 2 O and Mn 3 Fe(PO 4 )2.4H 2 In addition to O, the phosphorized crystal grains may contain manganese dihydrogen phosphate, manganese hydrogen phosphate and other components.
Illustratively, phosphating the steel with the phosphating solution includes: the steel material is immersed in the phosphating solution at a temperature of 90 to 94 ℃ (e.g., 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃ and the like) for a period of 3 to 5 minutes (e.g., 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, 5 minutes and the like).
Illustratively, the thickness of the phosphating film is 0.5 μm to 3 μm, for example 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, etc.
Illustratively, the method for corrosion protection treatment of steel material prior to phosphating the steel material with the phosphating solution further comprises: and applying a manganese monohydrogen phosphate colloid solution on the surface of the steel. By applying the manganese monohydrogen phosphate colloidal solution on the surface of the steel, colloidal particles in the manganese monohydrogen phosphate colloidal solution can be uniformly adsorbed on the surface of the steel, so that a large number of micro-cathode areas are formed on the surface of the steel to form phosphate crystal nuclei, the influence of physical or chemical non-uniformity existing on the surface state of the steel on the film forming process is eliminated, the uniform and rapid formation of crystals is promoted, the growth of large crystals is prevented, the crystals of the phosphating film are fine and compact, a phosphating film layer with uniform film thickness can be formed, and the phosphating treatment time is shortened.
By way of example, "applying a manganese monohydrogen phosphate colloidal solution to the surface of a steel material" may specifically include: the steel material is immersed in the manganese monohydrogen phosphate colloid solution for 20 to 40 seconds (for example, 30 seconds; illustratively, the content of manganese monohydrogen phosphate in the manganese monohydrogen phosphate colloid solution may be 0.1wt% to 4wt%, for example, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, etc.
Illustratively, the method of corrosion-protecting treatment of the steel material may further include, prior to applying the manganese monohydrogen phosphate colloidal solution to the surface of the steel material:
grinding the surface of the steel to remove rust on the surface of the steel;
treating the steel by adopting an alkaline degreasing agent to remove grease impurities on the surface of the steel;
the steel is treated with an acidic solution to remove metal oxides from the surface of the steel.
By way of example, "grinding the surface of the steel material" may specifically include: carrying out magnetic grinding on the surface of steel, wherein the adopted magnetic needle has the following size: the diameter is 0.4mm, the length is 10mm, the adopted grinding agent is neutral grinding agent, the grinding time is 3 minutes to 7 minutes (for example, 5 minutes), the grinding frequency is 15HZ to 35HZ (for example, 25 HZ), and the pH value of the grinding agent is 6 to 7 (for example, 6.5).
Illustratively, when the steel is treated with an alkaline degreasing agent, the alkaline degreasing agent includes sodium carbonate, sodium hydroxide, a surfactant (e.g., sodium dodecylbenzenesulfonate, etc.), and water, wherein the concentration of sodium carbonate is 35g/L to 45g/L (e.g., 40 g/L), the concentration of sodium hydroxide is 9g/L to 11g/L (e.g., 10 g/L), and the concentration of surfactant is 8ml/L to 12ml/L (e.g., 10 ml/L). Illustratively, the alkaline degreasing agent may have a temperature of 50 ℃ -70 ℃ (e.g., 60 ℃), and the treatment time may be 0.5 minutes-1.5 minutes (e.g., 1 minute).
By way of example, "treating the steel with an acidic solution" may specifically include: the steel is treated with oxalic acid solution in the concentration of 3wt% -5 wt% (e.g. 4 wt%) for 110-130 seconds (e.g. 120 seconds).
For example, the step of "washing the steel material with pure water" may be provided between any two adjacent steps such as "grinding the surface of the steel material", "treating the steel material with an alkaline degreasing agent", "treating the steel material with an acidic solution", "applying a manganese monohydrogen phosphate colloidal solution to the surface of the steel material" and "phosphating the steel material with a phosphating solution".
Illustratively, after the steel is phosphated with the phosphating solution, the following steps may be sequentially set:
washing the steel by adopting pure water to remove residual phosphating solution on the surface of the steel;
soaking the steel material in sodium carbonate solution with the concentration of 3 g/L-7 g/L (for example, 5 g/L) to neutralize acidic substances in the phosphating solution remained on the surface of the steel material, wherein the soaking time can be 30-120 seconds (for example, 60 seconds);
the steel is dried to remove water on the surface of the steel, the drying temperature can be 90 ℃ -100 ℃ (e.g. 95 ℃), and the drying time period can be 15 minutes-25 minutes (e.g. 20 minutes).
It should be noted that, referring to fig. 2, fig. 2 is a photomicrograph of the phosphated film prepared in the embodiment of the present application, it can be seen that the phosphated film is composed of a plurality of grains, and micropores are formed between adjacent grains.
S200, providing a sealing agent, and applying the sealing agent on the surface of the phosphating film so that the sealing agent enters micropores of the phosphating film.
Illustratively, the sealant may include mineral oil.
By way of example, "applying a sealer to a phosphating film surface" may specifically include: the steel is soaked in the sealing agent for 60 to 120 seconds (for example, 90 seconds).
When the sealant is mineral oil, the hydroxyl group is usually contained in the mineral oil, and the hydrogen element is contained in the phosphating film, so that a chemical bond can be formed between the hydroxyl group in the mineral oil and the hydrogen in the phosphating film, the mineral oil penetrates into micropores of the phosphating film in a chemical reaction film forming and physical film forming mode to form a film blocking microchannel, and the corrosion resistance of the phosphating film is further improved.
Illustratively, after the sealer is applied to the surface of the phosphate film, a step of drying the steel may be further provided to promote deposition of the sealer in the micropores, and the drying temperature may be 90 to 100 ℃ (e.g., 95 ℃) and the drying period may be 15 to 25 minutes (e.g., 20 minutes).
Referring to fig. 3, fig. 3 is a photograph of a steel product subjected to corrosion protection treatment in the embodiment of the present application, it can be seen that the appearance of the steel product is black after corrosion protection treatment, and compared with the conventional corrosion protection treatment process for steel products, the blackening treatment step can be omitted, thereby reducing the implementation cost of the process.
In summary, according to the corrosion-resistant treatment method for steel provided by the embodiment of the application, the phosphating solution is adopted to carry out phosphating treatment on the steel, a phosphating film is formed on the surface of the steel, and then a sealing agent is applied to the surface of the phosphating film, so that the sealing agent enters micropores of the phosphating film, the phosphating film can be utilized to play a corrosion-resistant effect, and the sealing agent can be utilized to fill the micropores in the phosphating film, so that the corrosion-resistant effect of the phosphating film is further improved, and the corrosion resistance of the steel is further improved; after the steel is treated by adopting the anti-corrosion treatment method of the steel, the obtained anti-corrosion steel can be subjected to neutral salt spray test for more than 60 hours without corrosion, and meanwhile, the surface of the obtained anti-corrosion steel is black, so that the blackening treatment step after conventional passivation is omitted, and the process implementation cost is reduced; in addition, hexavalent chromium ions are not generated in the anti-corrosion treatment process of the steel, the sewage treatment cost is low, and hexavalent chromium ions are not remained on the surface of the treated steel.
The embodiment of the application also provides a corrosion-resistant steel, wherein the surface of the corrosion-resistant steel is provided with a phosphating film, the phosphating film comprises a plurality of crystal grains, micropores are formed between the adjacent crystal grains, and a sealing agent is contained in the micropores.
The corrosion protection treatment method of the steel material provided in the present application will be described in the form of specific examples.
Example 1
Providing an ultra-high strength structural steel, which comprises 16 parts by weight of nickel, 8 parts by weight of cobalt, 3 parts by weight of molybdenum, 3 parts by weight of niobium, 0.5 part by weight of vanadium, 0.05 part by weight of carbon, 0.1 part by weight of oxygen and 69.35 parts by weight of iron, wherein the yield strength of the ultra-high strength structural steel can reach more than 1600Mpa, and the elongation is more than 5%, but the ultra-high strength structural steel fails to pass a 30-minute neutral salt spray test;
performing magnetic grinding on the surface of the steel to remove rust on the surface of the steel, and grinding the steel by a magnetic needle with the size of 0.4mm and the length of 10mm in a neutral grinding agent (pH value of 6.5) for 5min at the grinding frequency of 26HZ;
washing steel materials by pure water;
degreasing the surface of the steel by adopting an alkaline degreasing agent to remove impurities such as oil, wax and the like on the surface of the steel, wherein the alkaline degreasing agent is an aqueous solution, the concentration of sodium carbonate is 42g/L, the concentration of sodium hydroxide is 10g/L, the concentration of a surfactant is 10ml/L, the temperature of the alkaline degreasing agent is 60 ℃, and the treatment time is 1min;
washing steel materials by pure water;
soaking the steel material in oxalic acid solution with the concentration of 5wt% for 125 seconds;
washing steel materials by pure water;
soaking the steel in manganese dihydrogen phosphate colloid solution for 30 seconds;
washing steel materials by pure water;
soaking steel in a phosphating solution at 92 ℃ for 4 minutes, wherein the phosphating solution consists of 37 parts of manganese nitrate, 21 parts of phosphoric acid, 12 parts of manganese dihydrogen phosphate, 10 parts of nickel nitrate, 6 parts of citric acid, 5 parts of salicylic acid, 4 parts of ethylenediamine tetraacetic acid, 4.5 parts of sodium nitrite, 0.5 part of nitrous acid and 200 parts of water in parts by weight;
washing steel materials by pure water;
soaking the steel in sodium carbonate solution with the concentration of 5g/L for 60 seconds;
washing steel materials by pure water;
drying the steel at 95 ℃ for 20min;
soaking the steel in mineral oil for sealing, wherein the soaking time is 80 seconds;
and (3) drying the steel at the temperature of 95 ℃ for 20min.
Referring to fig. 4, fig. 4 is a photomicrograph of the surface of the steel material subjected to the corrosion protection treatment in example 1 of the present application. It can be seen that after the corrosion prevention treatment, the surface of the steel is covered with a layer of black phosphating film, and the corrosion resistance of the steel is greatly improved under the protection of the phosphating film and the sealing agent.
Referring to fig. 5, fig. 5 is a neutral salt spray test photograph of the steel material subjected to the corrosion protection treatment in example 1 of the present application. It can be seen that the surface of the steel product remains bright after 70 hours of the neutral salt spray test, and no rust signs appear, that is, the steel product subjected to the corrosion protection treatment in the embodiment 1 of the application has good corrosion resistance.
Example 2
In example 2, the composition of the phosphating solution is different from that of example 1, and the phosphating solution is composed of 35 parts by weight of manganese nitrate, 20 parts by weight of phosphoric acid, 10 parts by weight of manganese dihydrogen phosphate, 10 parts by weight of nickel nitrate, 7 parts by weight of citric acid, 6 parts by weight of salicylic acid, 5 parts by weight of ethylenediamine tetraacetic acid, 5 parts by weight of sodium nitrite, 2 parts by weight of nitrous acid and 200 parts by weight of water;
the result of the neutral salt spray test on the steel subjected to the corrosion prevention treatment shows that the surface of the steel still remains bright after the neutral salt spray test is performed for 80 hours, and no rust signs appear, that is, the steel subjected to the corrosion prevention treatment in the embodiment 2 of the application has good corrosion resistance.
Example 3
In example 3, the composition of the phosphating solution was 34 parts by weight of manganese nitrate, 21 parts by weight of phosphoric acid, 10 parts by weight of manganese dihydrogen phosphate, 12 parts by weight of nickel nitrate, 6 parts by weight of citric acid, 7 parts by weight of salicylic acid, 4 parts by weight of ethylenediamine tetraacetic acid, 5.5 parts by weight of sodium nitrite, 0.5 part by weight of nitrous acid, and 200 parts by weight of water;
the result of the neutral salt spray test on the steel after the corrosion prevention treatment shows that the surface of the steel still remains bright after the neutral salt spray test is performed for 60 hours, and no rust signs appear, that is, the steel after the corrosion prevention treatment in the embodiment 3 of the application has better corrosion resistance.
The method for corrosion-resistant treatment of steel, corrosion-resistant steel and phosphating solution provided in the examples of the present application are described in detail above. Specific examples are set forth herein to illustrate the principles and embodiments of the present application, with the description of the examples given above only to assist in understanding the present application. Meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.
Claims (10)
1. A method for corrosion-resistant treatment of steel material, comprising:
providing steel and phosphating solution, carrying out phosphating treatment on the steel by adopting the phosphating solution, and forming a phosphating film on the surface of the steel, wherein the phosphating film comprises a plurality of crystal grains, and micropores are formed between the adjacent crystal grains;
providing a blocking agent, and applying the blocking agent on the surface of the phosphating film so that the blocking agent enters micropores of the phosphating film.
2. The method for anticorrosive treatment of steel according to claim 1, wherein the phosphating solution comprises, in parts by weight: 31-39 parts of manganese nitrate, 18-22 parts of phosphoric acid, 8-12 parts of manganese dihydrogen phosphate, 7-13 parts of nickel nitrate, 6-8 parts of citric acid, 5-7 parts of salicylic acid, 4-6 parts of ethylenediamine tetraacetic acid, 4-6 parts of sodium nitrite, 1.5-2.5 parts of nitrous acid and 150-250 parts of water.
3. The method for corrosion protection treatment of steel according to claim 1, wherein said phosphating of said steel with said phosphating solution comprises: the steel is soaked in the phosphating solution, the temperature of the phosphating solution is 90-94 ℃, and the soaking time is 3-5 minutes.
4. The method for anticorrosive treatment of steel according to claim 1, wherein the thickness of the phosphated film is 0.5 μm to 3 μm.
5. The method for corrosion protection treatment of steel according to claim 1, wherein the sealer comprises mineral oil.
6. The method for corrosion protection treatment of steel material according to claim 1, wherein the steel material is an ultra-high strength structural steel comprising, in parts by weight: 14 to 18 parts of nickel, 6 to 10 parts of cobalt, 2 to 4 parts of molybdenum, 2 to 4 parts of niobium, 0.3 to 0.7 part of vanadium, 0 to 0.2 part of carbon, 0 to 0.2 part of oxygen and 66 to 72 parts of iron.
7. The method for anticorrosive treatment of a steel material according to claim 1, wherein the method for anticorrosive treatment of a steel material further comprises, before the steel material is phosphated with the phosphating solution: and applying a manganese monohydrogen phosphate colloid solution on the surface of the steel.
8. The method for the corrosion prevention treatment of a steel material according to any one of claims 1 to 7, characterized in that the method for the corrosion prevention treatment of a steel material further comprises, before the steel material is phosphated with the phosphating solution:
grinding the surface of the steel to remove rust on the surface of the steel;
treating the steel by adopting an alkaline degreasing agent to remove grease impurities on the surface of the steel;
and (3) treating the steel with an acidic solution to remove metal oxides on the surface of the steel.
9. A corrosion-resistant steel material, characterized in that the surface of the corrosion-resistant steel material is provided with a phosphating film, the phosphating film comprises a plurality of crystal grains, micropores are formed between adjacent crystal grains, and a sealing agent is contained in the micropores.
10. A phosphating solution, which is characterized by comprising, in parts by weight: 31-39 parts of manganese nitrate, 18-22 parts of phosphoric acid, 8-12 parts of manganese dihydrogen phosphate, 7-13 parts of nickel nitrate, 6-8 parts of citric acid, 5-7 parts of salicylic acid, 4-6 parts of ethylenediamine tetraacetic acid, 4-6 parts of sodium nitrite, 1.5-2.5 parts of nitrous acid and 150-250 parts of water.
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