CN114737189B - Method for producing a surface pretreatment layer - Google Patents
Method for producing a surface pretreatment layer Download PDFInfo
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- CN114737189B CN114737189B CN202210267437.6A CN202210267437A CN114737189B CN 114737189 B CN114737189 B CN 114737189B CN 202210267437 A CN202210267437 A CN 202210267437A CN 114737189 B CN114737189 B CN 114737189B
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- rust inhibitor
- pretreatment
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- 238000004519 manufacturing process Methods 0.000 title description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 39
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 34
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 34
- 239000000467 phytic acid Substances 0.000 claims abstract description 34
- 229940068041 phytic acid Drugs 0.000 claims abstract description 34
- 239000003112 inhibitor Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000005498 polishing Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 239000001433 sodium tartrate Substances 0.000 claims description 4
- 229960002167 sodium tartrate Drugs 0.000 claims description 4
- 235000011004 sodium tartrates Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 4
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 38
- 239000010959 steel Substances 0.000 abstract description 38
- 239000002131 composite material Substances 0.000 abstract description 18
- 238000002791 soaking Methods 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 229910000975 Carbon steel Inorganic materials 0.000 abstract 1
- 239000010962 carbon steel Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 51
- 238000005260 corrosion Methods 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 10
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a method for preparing a surface pretreatment layer, which comprises the steps of firstly preparing the pretreatment layer on the surface of a steel bar, namely grafting phytic acid and polyvinyl alcohol to prepare pretreatment liquid, doping whiskers, soaking the surface of carbon steel in the pretreatment liquid to prepare the pretreatment layer, taking out and drying. And secondly, soaking the steel bars with the pretreatment layers prepared on the surfaces of the first step in a rust inhibitor solution, taking out and drying. The phytic acid composite pretreatment layer with protective performance is prepared, whiskers in the pretreatment layer are firmly combined with a substrate, a unique porous skeleton structure with micron-sized thickness is formed, the specific surface area of the structure is large, a rust inhibitor can be effectively loaded, and the self-repairing performance of the pretreatment layer is endowed. The preparation process is simple, low in cost, environment-friendly and suitable for industrial production and application.
Description
Technical Field
The invention relates to material surface treatment, in particular to a method for preparing a surface pretreatment layer.
Background
The problem of rust on the steel reinforcement is one of the most important reasons for affecting the durability of reinforced concrete structures. Structural cracks, protective layer peeling and other damage caused by corrosion can cause huge economic loss and life and property safety in severe cases. Among the many anti-corrosion measures, surface coating protection technology is a relatively wide and effective means at present. The traditional coating system consists of a pretreatment layer (chemical conversion layer) on the surface of the steel bar matrix and a protective organic coating covered on the pretreatment layer, and in order to improve the corrosion resistance of the coating system, a rust inhibitor is generally doped in the pretreatment layer or the organic coating. The pretreatment layer has good compactness, strong adhesiveness and rough and porous structure, and provides sufficient feasibility for the loading of the rust inhibitor. However, conventional pretreatment layer technologies such as phosphate passivation and chromate passivation can cause environmental pollution, toxicity, harm and the like. In addition, the thickness of the pretreatment layer only reaches the nanometer or micro-nanometer level under the influence of the traditional material process, so that the loading amount of the rust inhibitor in the pretreatment layer is limited.
In order to overcome the limitation of the conditions, students at home and abroad respectively adopt green environment-friendly materials and porous functional materials to research and explore the problems of innocuity, high efficiency, corrosion resistance and the like of the pretreatment layer. Patent CN11235576B discloses a method for constructing a porous organic pretreatment layer, which comprises the steps of preparing a metal surface pretreatment layer by grafting one or more green nontoxic organic acids with a hydroxylation-rich polymer, and loading a rust inhibitor to improve the resistance performance of a coating system. According to the invention, although a green material is adopted to prepare a harmless pretreatment layer, and the layer thickness and the loading capacity of the rust inhibitor are improved to a certain extent, the pretreatment layer still only depends on the pores and cracks existing in the pretreatment layer, and the rust inhibitor is loaded on the nano scale, so that the corrosion resistance of a coating system is limited. Patent CN10810247B discloses a method for preparing a coating by loading a rust inhibitor with modified silicon dioxide, wherein mesoporous silicon dioxide loaded with the rust inhibitor is doped into the coating by a solvothermal method, and when the coating is broken, the rust inhibitor is released from the silicon dioxide and adsorbed on the metal surface, so that the effect of healing the defects of the coating is achieved. Although the invention can effectively release the rust inhibitor during metal corrosion, the preparation method is complex, and the purpose can be achieved by multi-step reaction.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for preparing a surface pretreatment layer, which solves the problems of limited load rust inhibitor, complex method, and insufficient stability and compactness between a substrate and the pretreatment layer.
The technical scheme is as follows: the method for preparing the surface pretreatment layer comprises the following steps:
(1) Polishing, polishing and degreasing the surface of the substrate;
(2) Mixing deionized water, phytic acid, polyvinyl alcohol and whiskers, stirring at a preset temperature to obtain a mixed solution, cooling to normal temperature, and regulating the pH to be 8-10 to obtain a pretreatment solution;
(3) And fully immersing the substrate in the pretreatment liquid, drying, immersing in the rust inhibitor solution, and drying to obtain the surface pretreatment layer.
Preferably, in the step (1), the surface of the substrate is polished step by 400-1200# abrasive paper, polished by polishing solution, and subjected to ultrasonic washing with deionized water and ethanol for degreasing and drying with cold air.
In the step (2), the mass ratio of the ionized water to the phytic acid to the polyvinyl alcohol to the whisker is as follows: 500:5:1:1 to 200:6:2:1.
1-3 G of phytic acid, 0.2-1 g of polyvinyl alcohol and 0.2-0.5 g of whisker are added into 100mL of deionized water in the step (2).
And (3) stirring in the step (2) in a water bath at 75-85 ℃ for 3-7 h.
The whisker in the step (2) is at least one of potassium titanate, magnesium sulfate, zinc oxide and magnesium borate.
And (3) adjusting the pH value by adopting hydroxide in the step (2), wherein the hydroxide is at least one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
And (3) stirring the substrate fully immersed in the pretreatment liquid at a stirring temperature of 25+/-3 ℃ and a stirring speed of 100-200 r/min.
The rust inhibitor is at least one of sodium tartrate, sodium molybdate, benzotriazole and trisodium phosphate.
The concentration of the rust inhibitor in the rust inhibitor solution is 0.01-0.05 mol/L, the stirring time is 0.5-2 h when the rust inhibitor solution is immersed into the rust inhibitor solution for stirring, the stirring temperature is 25+/-3 ℃, and the stirring speed is 100-200 r/min.
The beneficial effects are that: the invention utilizes the strong chelating ability and coordination function of the phytic acid grafting liquid on the metal matrix to fix the whisker on the surface of the steel bar and loads the rust inhibitor to prepare the composite pretreatment layer. The whisker material not only provides a porous framework structure with micron-sized thickness for the pretreatment layer, but also improves the stability and compactness between the matrix and the pretreatment layer, thereby improving the corrosion resistance of the pretreatment layer. In addition, the porous skeleton structure formed by overlapping the whiskers has large specific surface area, and can effectively load a large amount of rust inhibitor, so that the corrosion-resistant self-repairing performance of the pretreatment layer is further provided. Finally, the preparation process of the pretreatment layer is simple and convenient, low in cost, environment-friendly and suitable for industrial production and application.
Drawings
FIG. 1 is an XRD pattern of a steel bar sample prepared in comparative example and example 1, which had a pretreatment layer but was not loaded with a rust inhibitor;
FIG. 2 is an SED-EDS diagram of a steel bar sample prepared in example 1 with a pretreatment layer but without a rust inhibitor, wherein (a) and (b) are SEM images and (c) is an EDS spectrum;
FIG. 3 is a graph showing the comparison of the electrochemical impedance spectra Nyquist of the steel bar samples of comparative examples and examples 1-4, prepared with a pretreatment layer and loaded with a rust inhibitor, immersed in a saturated calcium hydroxide solution containing 3.5wt% sodium chloride for 1 day;
FIG. 4 is an equivalent circuit diagram fitting EIS data;
Fig. 5 is a surface corrosion profile of the steel bar samples prepared in comparative examples and examples 1 to 4, which were pretreated and loaded with rust inhibitor, after soaking in a saturated calcium hydroxide solution containing 3.5wt% sodium chloride for 40 days.
Detailed Description
The invention will be further described with reference to examples and figures.
Example 1
And (3) polishing the surface of the steel bar step by using 400-1200# sand paper, polishing by using polishing liquid, flushing by using deionized water, performing ultrasonic treatment by using alcohol for 5 minutes, and drying by using cold air for later use. 100mL of deionized water is added into a flask, 3g of phytic acid, 1g of polyvinyl alcohol and 0.5g of potassium titanate whisker are added, the mixed solution is stirred in a water bath at 85 ℃ for 5h, the stirring speed is 1000r/min, the mixture is cooled and kept stand to normal temperature, and then the mixture is regulated to a weak alkaline environment with pH 10 by sodium hydroxide, so as to obtain a pretreatment liquid. Soaking the treated steel bar surface in the prepared pretreatment liquid, stirring for 60min at 25 ℃ at a stirring rate of 100r/min, taking out the steel bar of the prepared phytic acid pretreatment layer, and drying with cold air.
Fig. 1 is an XRD comparison pattern of a bare substrate rebar sample and rebar prepared using a pretreatment solution, showing a distinct PTW diffraction peak. Fig. 2 is a scanning electron micrograph of a pre-treated layer of the surface of the steel bar prepared with the pre-treatment solution, showing a skeleton structure with obvious stacked whiskers, being coarse and porous, and the P element of EDS results demonstrating the presence of phytic acid or phytic acid grafted polyvinyl alcohol. And then placing the reinforcing steel bars into 100mL of sodium tartrate solution with the concentration of 0.02mol/L, soaking for 60min, stirring at the stirring temperature of 25 ℃ at 100r/min, taking out the reinforcing steel bars of the prepared phytic acid composite pretreatment layer, and drying with cold air. To evaluate the corrosion resistance of the phytic acid composite pretreatment layer, the bare substrate steel bar sample and the steel bar sample prepared with the phytic acid composite pretreatment layer were respectively immersed in a saturated calcium hydroxide solution containing 3.5wt% sodium chloride for 1 day, and the rust resistance was tested by Electrochemical Impedance Spectroscopy (EIS). Specific results as shown in fig. 3a, the corrosion resistance of the sample of example 1 loaded with sodium tartrate was significantly improved compared to the comparative example. In order to explore the long-term corrosion behavior of the steel bar sample of the phytic acid composite pretreatment layer, the surface corrosion morphology of the sample after soaking for 40 days is observed by an optical microscope, the specific result is shown in fig. 5b, and compared with the bare substrate steel bar sample in fig. 5a, the surface of the sample of the example 1 is observed to be smoother and has a small number of pitting.
Example 2
And (3) polishing the surface of the steel bar step by using 400-1200# sand paper, polishing by using polishing liquid, flushing by using deionized water, performing ultrasonic treatment by using alcohol for 5 minutes, and drying by using cold air for later use. 100mL of deionized water is added into a flask, 2g of phytic acid, 0.5g of polyvinyl alcohol and 0.5g of potassium titanate whisker are added, the mixed solution is stirred in a water bath at 80 ℃ for 7h, the stirring speed is 800r/min, the mixture is cooled and kept stand to normal temperature, and then the mixture is regulated to a weak alkaline environment with pH 9 by sodium hydroxide, so as to obtain a pretreatment liquid. Soaking the treated steel bar surface in the prepared pretreatment liquid, stirring for 60min at 25 ℃ at a stirring rate of 100r/min, taking out the steel bar of the prepared phytic acid pretreatment layer, and drying with cold air. And then placing the reinforcing steel bars into 100mL of sodium molybdate solution with the concentration of 0.03mol/L, soaking for 60min, stirring at the stirring temperature of 25 ℃ at 100r/min, taking out the reinforcing steel bars of the prepared phytic acid composite pretreatment layer, and drying with cold air. To evaluate the corrosion resistance of the phytic acid composite pretreatment layer, the bare substrate steel bar sample and the steel bar sample prepared with the phytic acid composite pretreatment layer were respectively immersed in a saturated calcium hydroxide solution containing 3.5wt% sodium chloride for 1 day, and the rust resistance was tested by Electrochemical Impedance Spectroscopy (EIS). Specific results as shown in fig. 3b, the corrosion resistance of the sample of example 2 loaded with sodium molybdate was significantly improved as compared with the comparative example. In order to explore the long-term corrosion behavior of the steel bar sample of the phytic acid composite pretreatment layer, the surface corrosion morphology of the sample after soaking for 40 days is observed by an optical microscope, the specific result is shown in fig. 5c, and compared with the bare substrate steel bar sample in fig. 5a, the surface of the sample of the example 2 is observed to be smoother and flatter.
Example 3
And (3) polishing the surface of the steel bar step by using 400-1200# sand paper, polishing by using polishing liquid, flushing by using deionized water, performing ultrasonic treatment by using alcohol for 5 minutes, and drying by using cold air for later use. 100mL of deionized water is added into a flask, 1g of phytic acid, 0.2g of polyvinyl alcohol and 0.2g of potassium titanate whisker are added, the mixed solution is stirred in a water bath at 75 ℃ for 4 hours, the stirring speed is 800r/min, the mixture is cooled and kept stand to normal temperature, and then the mixture is regulated to a weak alkaline environment with pH 9 by sodium hydroxide, so as to obtain a pretreatment liquid. Soaking the treated steel bar surface in the prepared pretreatment liquid, stirring for 60min at 25 ℃ at a stirring rate of 100r/min, taking out the steel bar of the prepared phytic acid pretreatment layer, and drying with cold air. And then placing the reinforcing steel bars into 100mL of benzotriazole solution with the concentration of 0.01mol/L, soaking for 30min, stirring at the stirring temperature of 25 ℃ at 100r/min, taking out the reinforcing steel bars of the prepared phytic acid composite pretreatment layer, and drying with cold air. To evaluate the corrosion resistance of the phytic acid composite pretreatment layer, the bare substrate steel bar sample and the steel bar sample prepared with the phytic acid composite pretreatment layer were respectively immersed in a saturated calcium hydroxide solution containing 3.5wt% sodium chloride for 1 day, and the rust resistance was tested by Electrochemical Impedance Spectroscopy (EIS). Specific results As shown in FIG. 3c, the corrosion resistance of the benzotriazole-loaded sample of example 3 was significantly improved as compared to the comparative example. In order to explore the long-term corrosion behavior of the steel bar sample of the phytic acid composite pretreatment layer, the surface corrosion morphology of the sample after soaking for 40 days is observed by an optical microscope, the specific result is shown in fig. 5d, and compared with the bare substrate steel bar sample in fig. 5a, more pitting is observed on the surface of the sample in example 3, but the corrosion degree is still far lower than that of the comparative example.
Example 4
And (3) polishing the surface of the steel bar step by using 400-1200# sand paper, polishing by using polishing liquid, flushing by using deionized water, performing ultrasonic treatment by using alcohol for 5 minutes, and drying by using cold air for later use. 100mL of deionized water is added into a flask, 2g of phytic acid, 1g of polyvinyl alcohol and 0.5g of potassium titanate whisker are added, the mixed solution is stirred in a water bath at 85 ℃ for 6h, the stirring speed is 1500r/min, the mixture is cooled and kept stand to normal temperature, and then the mixture is regulated to a weak alkaline environment with pH 10 by sodium hydroxide, so as to obtain a pretreatment liquid. Soaking the treated steel bar surface in the prepared pretreatment liquid, stirring for 60min at 25 ℃ at the stirring speed of 200r/min, taking out the steel bar of the prepared phytic acid pretreatment layer, and drying with cold air. And then placing the reinforcing steel bars into 100mL trisodium phosphate solution with the concentration of 0.05mol/L, soaking for 60min, stirring at the stirring temperature of 25 ℃ at 100r/min, taking out the reinforcing steel bars of the prepared phytic acid composite pretreatment layer, and drying with cold air. To evaluate the corrosion resistance of the phytic acid composite pretreatment layer, the bare substrate steel bar sample and the steel bar sample prepared with the phytic acid composite pretreatment layer were respectively immersed in a saturated calcium hydroxide solution containing 3.5wt% sodium chloride for 1 day, and the rust resistance was tested by Electrochemical Impedance Spectroscopy (EIS). The specific results are shown in FIG. 3d, and the corrosion resistance of the sample of example 4 loaded with trisodium phosphate is significantly improved compared with the comparative example. In order to explore the long-term corrosion behavior of the steel bar sample of the phytic acid composite pretreatment layer, the surface corrosion morphology of the sample after soaking for 40 days is observed by an optical microscope, the specific result is shown in fig. 5e, and compared with the bare substrate steel bar sample in fig. 5a, the surface of the sample of the example 4 is observed to be smoother, and no pitting is obvious.
The EIS results of examples 1-4 were fitted by the equivalent circuit in fig. 4, the fitting results are shown in table 1,
TABLE 1
As can be seen from table 1, the rust inhibition efficiency of example 1 was raised to 92.93%, the rust inhibition efficiency of example 2 was raised to 91.21%, the rust inhibition efficiency of example 3 was raised to 82.99%, and the rust inhibition efficiency of example 4 was raised to 89.22%.
Claims (7)
1. A method of preparing a surface pretreatment layer, comprising the steps of:
(1) Grinding, polishing and degreasing the surface of the metal substrate;
(2) Mixing deionized water, phytic acid, polyvinyl alcohol and whiskers, stirring at a preset temperature to obtain a mixed solution, cooling to normal temperature, and then adjusting the pH to be 8-10 to obtain a pretreatment solution;
(3) Fully immersing a metal substrate in the pretreatment liquid, drying, immersing in the rust inhibitor solution, and drying to obtain a surface pretreatment layer;
In the step (2), 1-3 g of phytic acid, 0.2-1 g of polyvinyl alcohol and 0.2-0.5 g of whisker are added into 100 mL of deionized water; the whisker is at least one of potassium titanate, magnesium sulfate, zinc oxide and magnesium borate.
2. The method for preparing a surface pretreatment layer according to claim 1, wherein in the step (1), the surface of the substrate is polished step by step with 400-1200 # abrasive paper, polished with a polishing liquid, rinsed with deionized water multiple times and dried with cold air.
3. The method of preparing a surface pretreatment layer according to claim 1, wherein in the step (2), 3 to 7 h are stirred in a water bath at 75 to 85 ℃.
4. The method for preparing a surface pretreatment layer according to claim 1, wherein in the step (2), a hydroxide is used to adjust the pH, and the hydroxide is at least one of sodium hydroxide, calcium hydroxide, and potassium hydroxide.
5. The method for preparing a surface pretreatment layer according to claim 1, wherein the stirring temperature is 25±3 ℃ and the stirring speed is 100 to 200 r/min when the substrate is fully immersed in the pretreatment liquid in the step (3).
6. The method of preparing a surface pretreatment layer according to claim 1, wherein the rust inhibitor is at least one of sodium tartrate, sodium molybdate, benzotriazole, trisodium phosphate.
7. The method for preparing a surface pretreatment layer according to claim 1, wherein the concentration of the rust inhibitor in the rust inhibitor solution is 0.01-0.05 mol/L, the stirring time is 0.5-2 h when the rust inhibitor solution is immersed and stirred, the stirring temperature is 25+ -3 ℃, and the stirring speed is 100-200 r/min.
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