CN113088853A - Hot galvanizing process for high-strength fastener - Google Patents

Hot galvanizing process for high-strength fastener Download PDF

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Publication number
CN113088853A
CN113088853A CN202110326911.3A CN202110326911A CN113088853A CN 113088853 A CN113088853 A CN 113088853A CN 202110326911 A CN202110326911 A CN 202110326911A CN 113088853 A CN113088853 A CN 113088853A
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strength fastener
strength
fastener
dipping
pickling
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CN113088853B (en
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吴应平
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Zhejiang Hangfeng Tower Co ltd
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Zhejiang Hangfeng Tower Co ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/48Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/48Chemical 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
    • C23C22/50Treatment of iron or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08Iron or steel
    • C23G1/088Iron or steel solutions containing organic acids

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemically Coating (AREA)

Abstract

The application relates to the technical field of galvanizing processes, and particularly discloses a hot galvanizing process for a high-strength fastener, which comprises the following steps: after degreasing, first washing, acid washing and second washing, dipping the high-strength fastener in a plating assistant agent, controlling the temperature to be 40-55 ℃ and the dipping time to be 30-90s, drying the dipped high-strength fastener after dipping, then dipping the high-strength fastener in zinc liquid, controlling the temperature of the zinc liquid to be 420-470 ℃ and the dipping time to be 300-350s, taking out the dipped high-strength fastener from a plating solution, cooling the high-strength fastener and then dipping the high-strength fastener in a passivation solution for 10-40s, wherein the dipping temperature is 20-35 ℃, and then washing the high-strength fastener for the third time to obtain the passivated high-strength fastener; then drying, checking and packaging to obtain a finished product; the plating assistant agent comprises the following raw materials in percentage by weight: 0.5-1.5% of platycodon grandiflorum powder, 0.1-1% of hydroxypropyl methyl cellulose, 0.2-0.8% of allyl alcohol polyoxyethylene polyoxypropylene ether, 8-20% of zinc chloride, 6-15% of ammonium chloride and the balance of deionized water; the high-strength fastener obtained by the process has the advantage of good wear resistance.

Description

Hot galvanizing process for high-strength fastener
Technical Field
The application relates to the technical field of galvanizing processes, in particular to a hot galvanizing process for a high-strength fastener.
Background
Hot galvanizing is a process method for dipping a high-strength fastener into molten metal liquid to form a metal coating on the surface of the high-strength fastener, and is generally applied to steel materials such as high-strength fasteners with high shearing resistance and yield coefficients to endow the high-strength fasteners with good corrosion resistance.
The publication No. CN107513681A discloses a hot-dip galvanizing process with the publication time of 2019, 12 months and 20 days, which comprises the following steps: first step, deoiling: pouring the workpiece into a mixed solution of 10-12g/L sodium carbonate and 12-15g/L sodium hydroxide, wherein the temperature of the solution is 90-100 ℃, and the workpiece is completely soaked; secondly, pickling, namely pickling the workpiece in 15% -20% sulfuric acid solution for 5-10min at the pickling temperature of 30-50 ℃, and washing the workpiece for 2-3min with clean water after pickling; thirdly, cleaning the workpiece by warm water at 50-60 ℃; and fourthly, dipping the plating assistant solution, namely putting the workpiece into zinc chloride-ammonium chloride aqueous solution for dipping at the dipping temperature of 60-70 ℃ for 1-3 min.
Through the related technology, firstly, the workpiece is degreased and pickled, impurities on the surface of the workpiece are removed, and substances such as ferric salt and the like remained on the surface of the workpiece after pickling are removed by warm water, but the cleaning effect is poor, so that the workpiece cannot be in full contact with zinc liquid, the adhesion between a zinc coating and the workpiece is poor, and the wear resistance of the zinc coating on the surface of the hot-galvanized workpiece is poor.
Disclosure of Invention
In order to improve the wear resistance of the high-strength fastener after hot galvanizing, the hot galvanizing process for the high-strength fastener is provided.
In a first aspect, the present application provides a hot galvanizing process for a high-strength fastener, which adopts the following technical scheme: a hot galvanizing process of a high-strength fastener comprises the following steps:
s1, degreasing the high-strength fastener, washing with water for the first time, pickling, washing with water for the second time to obtain a pretreated high-strength fastener;
s2, dipping the pre-treated high-strength fastener in a plating assistant agent, controlling the temperature to be 40-55 ℃ and the dipping time to be 30-90S, and obtaining the plated high-strength fastener after dipping;
s3, drying the plating-assisted high-strength fastener, immersing the fastener in zinc liquid, controlling the temperature of the zinc liquid at 420-;
s4, cooling the galvanized high-strength fastener to 20-40 ℃, immersing the fastener into passivation solution for 10-40S at 20-35 ℃, and washing for the third time to obtain the passivated high-strength fastener;
s5, drying, inspecting and packaging the passivated high-strength fastener to obtain a finished product;
the plating assistant agent comprises the following raw materials in percentage by weight:
0.5 to 1.5 percent of platycodon grandiflorum powder;
0.1 to 1 percent of hydroxypropyl methyl cellulose;
0.2 to 0.8 percent of allyl alcohol polyoxyethylene polyoxypropylene ether;
8-20% of zinc chloride;
6-15% of ammonium chloride;
the balance of deionized water.
By adopting the technical scheme, firstly, the high-strength fastener is subjected to degreasing, acid washing, water washing and other steps, impurities such as grease and the like on the surface of the high-strength fastener are removed, and then the high-strength fastener is soaked in the plating assistant agent, so that the high-strength fastener is conveniently combined with the zinc liquid at the later stage, and the zinc liquid is effectively attached to the surface of the high-strength fastener; the plating assistant agent is formed by combining inorganic matters, organic matters and natural substances, and impurities such as ferric salt and the like on the surface of the high-strength fastener are fully cleaned, so that the high-strength fastener is tightly combined with zinc liquid, and the wear resistance of the high-strength fastener is enhanced; after natural substances of platycodon grandiflorum powder, hydroxypropyl methylcellulose and allyl alcohol polyoxyethylene polyoxypropylene ether are combined, the surface tension of zinc liquid is reduced, so that the zinc liquid is easier to attach to the surface of a high-strength fastener; the ammonium chloride and the zinc chloride act with the zinc liquid to reduce the surface tension of the zinc liquid surface, further remove impurities such as ferric salt and the like which are not removed from the surface of the high-strength fastener, and enhance the adhesive force of the zinc liquid, thereby enhancing the wear resistance of the zinc coating on the surface of the high-strength fastener.
Preferably, the step S1 of degreasing specifically comprises:
a1, soaking the high-strength fastener in 3-6% sodium hydroxide solution at 30-50 deg.C for 3-5 min;
a2, soaking the high-strength fastener obtained in the step A1 in the degreasing agent at 70-80 ℃ for 3-5 min.
By adopting the technical scheme, firstly, sodium hydroxide is utilized to emulsify the grease, then the degreasing agent is added to further degrease the grease, so that the plating assistant agent and the zinc liquid can be better attached to the surface of the high-strength fastener in the later period, and the pollution of impurities such as the grease to the zinc liquid can be reduced.
Preferably, the degreasing agent in the step a2 is composed of the following raw materials by weight:
3-6% of rice hull powder;
0.5 to 2 percent of sodium carbonate;
zeolite powder 0.5-1.5%;
tartaric acid 0.1-0.4%;
1-3% of isooctyl alcohol polyoxyethylene ether;
the balance of deionized water.
By adopting the technical scheme, after the sodium carbonate and the isooctanol polyoxyethylene ether interact, impurities such as grease on the surface of the high-strength fastener are softened and wetted, the zeolite powder, the rice hull powder, the tartaric acid and the isooctanol polyoxyethylene ether are cooperatively matched, and the grease which is prevented from being removed is attached to the surface of the high-strength fastener again, so that the binding force between the zinc liquid and the high-strength fastener is enhanced and the wear resistance of a zinc coating on the surface of the high-strength fastener is enhanced when the high-strength fastener is subjected to plating assisting and galvanizing in the later period.
Preferably, in the step a2, the high-strength fastener is stirred while being soaked in the degreasing agent, and the stirring speed is 100-400 r/min.
Through adopting above-mentioned technical scheme, the high strength fastener stirs when soaking in the degreasing agent, increases the chance of degreasing agent and high strength fastener surface contact to get rid of material such as the surperficial grease of high strength fastener fast effectively, make high strength fastener surface bright and clean, impurity-free, thereby make things convenient for the later stage to help and plate, make the zinc liquid effectively adhere to on high strength fastener surface, thereby give the better wear resistance of high strength fastener.
Preferably, the acid washing in step S1 includes the following specific steps: soaking the high-strength fastener after the first washing in a pickling agent for pickling, wherein the pickling temperature is 20-35 ℃, and the pickling time is 5-10 min; the pickling agent is prepared from the following raw materials in percentage by weight:
25-35% of hydrochloric acid;
3-6% of sulfuric acid;
0.4 to 0.8 percent of carboxyethyl sulfosuccinate;
1-3% of polyglutamic acid;
the balance of deionized water.
Through adopting above-mentioned technical scheme, after the degrease and washing, carry out the pickling to high strength fastener, material such as iron scale on high strength fastener surface is got rid of in hydrochloric acid and sulphuric acid cooperation, and carboxyethyl thiosuccinic acid and polyglutamic acid cooperation prevent that the impurity of getting rid of from adhering once more on high strength fastener surface, further improve impurity removal efficiency, strengthen the wear resistance on high strength fastener surface galvanizing coat.
Preferably, in the step S3, the dipped high-strength fastener is lifted out of the plating solution, and the lifting speed of the high-strength fastener is controlled to be 1-2.5 m/min.
By adopting the technical scheme, if the lifting speed is high, the zinc coating on the surface of the high-strength fastener is uneven easily, and the surface quality is poor; the lifting speed is too slow, so that an excessively thick zinc coating is easily formed, on one hand, the cost is increased, and on the other hand, the uniformity of the zinc coating is easily poor; when the lifting speed is controlled within the range, the cost is saved, and meanwhile, a uniform zinc coating is formed on the surface of the high-strength fastener, so that the high-strength fastener is endowed with better wear resistance.
Preferably, the passivation solution comprises the following raw materials in parts by weight:
2-6% of nitrate;
1-4% of nano aluminum sol;
3-10% of acid cosolvent;
0.5-2% of honeysuckle extract;
0.2 to 0.8 percent of sodium dodecyl benzene sulfonate;
the balance of deionized water.
By adopting the technical scheme, the nitrate is matched with the acidic cosolvent, the honeysuckle extract and the sodium dodecyl benzene sulfonate to effectively passivate the surface of the zinc coating of the high-strength fastener, so that the wear resistance of the zinc coating is enhanced on one hand, and the surface of the high-strength fastener is prevented from being corroded on the other hand; after the nano aluminum sol and the honeysuckle extract are combined, the wear resistance of the surface of the galvanized layer of the high-strength fastener is enhanced.
Preferably, the acidic cosolvent comprises at least one of citric acid and acetic acid.
By adopting the technical scheme, one or two of citric acid and acetic acid are preferably selected as acidic cosolvent, and after the acidic cosolvent is combined with substances such as nitrate, nano-alumina sol and the like in passivation solution, the wear resistance of the surface coating of the high-strength fastener is enhanced while passivation is rapidly carried out.
In summary, the present application has the following beneficial effects:
1. because the method firstly removes the grease on the surface of the high-strength fastener by degreasing, pickling and other steps, the later combination with the zinc liquid is convenient; the plating assistant agent is added with substances such as platycodon root powder, hydroxypropyl methyl fiber, allyl alcohol polyoxyethylene polyoxypropylene ether and the like, so that the surface tension of zinc liquid is reduced, impurities such as ferric salt and the like on the surface of a workpiece are removed, the zinc liquid is more easily attached to the surface of a high-strength fastener, and the wear resistance of a zinc coating on the surface of the high-strength fastener is enhanced.
2. In the application, a degreasing step is preferably selected, substances such as rice hull powder and zeolite powder are added into a degreasing agent and stirred, impurities such as grease on the surface of the high-strength fastener are softened and wetted, the grease is removed, and the removed impurities such as the grease are prevented from being attached to the surface of the high-strength fastener again, so that the binding force between the zinc liquid and the high-strength fastener is enhanced, and the wear resistance of a zinc coating on the surface of the high-strength fastener is enhanced; the components of the pickling agent are preferably selected, the polyglutamic acid is added into the pickling agent and is matched with carboxyethyl sulfosuccinate, so that the impurity removal efficiency is further improved, and the wear resistance of a zinc coating on the surface of the high-strength fastener is enhanced; the high-strength fastener is preferably raised by the plating solution speed, and a uniform zinc coating is formed on the surface of the high-strength fastener, so that the high-strength fastener is endowed with better wear resistance.
3. The nano aluminum sol and the honeysuckle extract are added into the passivation solution, so that on one hand, the nano aluminum sol and the honeysuckle extract are effectively matched with nitrate and an acidic cosolvent to perform effective passivation and enhance the corrosion resistance of the high-strength fastener, and on the other hand, the wear resistance of a zinc layer on the surface of the high-strength fastener is enhanced.
Detailed Description
The present application is described in further detail below.
The components and manufacturers in the examples are shown in Table 1.
TABLE 1 Components and manufacturers
Figure BDA0002994986030000051
Examples
Example 1:
a hot galvanizing process for a high-strength fastener comprises the following specific components by weight as shown in Table 2, and is prepared by the following steps:
s1, mixing and stirring sodium carbonate, zeolite powder, tartaric acid, isooctyl alcohol polyoxyethylene ether and deionized water at the stirring speed of 1000r/min, and uniformly stirring to obtain the degreasing agent; mixing and stirring hydrochloric acid, sulfuric acid, carboxyethyl sulfosuccinate and deionized water at the stirring speed of 900r/min, and uniformly stirring to obtain a pickling agent; mixing and stirring platycodon grandiflorum powder, hydroxypropyl methylcellulose, allyl alcohol polyoxyethylene polyoxypropylene ether, ammonium chloride, zinc chloride and deionized water at the stirring speed of 1000r/min, and uniformly stirring to obtain a plating assistant; mixing and stirring nitrate (sodium nitrate), nano aluminum sol, acidic cosolvent, sodium dodecyl benzene sulfonate and deionized water at the stirring speed of 1100r/min, and uniformly stirring to obtain the passivation solution.
S2, soaking the high-strength fastener (steel washer is selected) in the degreasing agent at 70 ℃ for 5 min; after the first washing, soaking the fastener into a pickling agent for pickling, wherein the pickling temperature is 35 ℃, the pickling time is 5min, and after the second washing, obtaining a pretreated high-strength fastener;
s3, dipping the pre-treated high-strength fastener in a plating assistant agent, controlling the temperature to be 55 ℃ and the dipping time to be 30S, and obtaining the plated high-strength fastener after dipping;
s4, drying the high-strength fastener after plating assistance, immersing the high-strength fastener in zinc liquid, controlling the temperature of the zinc liquid to be 420 ℃ and the time of immersing the high-strength fastener in the zinc liquid to be 350S, extracting the immersed high-strength fastener out of the plating solution at the extraction speed of 3m/min, and obtaining the galvanized high-strength fastener by the plating solution;
s5, cooling the galvanized high-strength fastener to 40 ℃, immersing the galvanized high-strength fastener into passivation solution for 10S at 35 ℃, and washing the galvanized high-strength fastener for the third time to obtain the passivated high-strength fastener;
and S6, drying, inspecting and packaging the passivated high-strength fastener to obtain a high-strength fastener finished product.
Example 2 a hot galvanizing process for a high-strength fastener, which is different from example 1 in the specific components and weights of a degreasing agent, a pickling agent, a plating assistant agent and a passivating solution, and the specific components and weights are included as shown in table 2.
Example 3 a hot galvanizing process for a high-strength fastener, which is different from example 1, in step S2, the high-strength fastener is immersed in a sodium hydroxide solution with a concentration of 3%, the temperature is controlled at 50 ℃, the immersion time is 3min, and then the high-strength fastener is immersed in a degreasing agent, wherein specific components and weights of the components are shown in table 2.
Example 4 a hot galvanizing process for a high-strength fastener, which is different from example 3, in that in step S2, the high-strength fastener is soaked in a sodium hydroxide solution with a concentration of 6%, the temperature is controlled at 30 ℃, the soaking time is 5min, and then the high-strength fastener is soaked in a degreasing agent, wherein specific components and weights are shown in table 2.
Examples 5-6 a hot galvanizing process for high-strength fasteners, which is different from example 4, in that rice hull powder was added to a degreasing agent in step S1, and the specific components and weights thereof were as shown in table 2.
Example 7 a hot dip galvanizing process for a high-strength fastener, which is different from example 4 in that the high-strength fastener is stirred at a stirring speed of 100r/min while being immersed in a degreasing agent.
Example 8 a hot dip galvanizing process for a high strength fastener, which is different from example 7 in that the high strength fastener is stirred at a stirring speed of 400r/min while being immersed in a degreasing agent.
Examples 9-10 a hot dip galvanizing process for high strength fasteners, which is different from example 1 in that polyglutamic acid is added to an acid pickling agent in step S1, and the specific components and weights thereof are shown in table 2.
Example 11: a hot galvanizing process for a high-strength fastener is different from that of the embodiment 1 in that the lifting speed in the step S4 is 1 m/min.
Example 12: a hot galvanizing process for a high-strength fastener is different from that of the embodiment 1 in that the lifting speed in the step S4 is 2.5 m/min.
Examples 13-14 a hot dip galvanizing process for high strength fasteners, which is different from example 1 in that, in step S1, a honeysuckle flower extract was added to a passivation solution, including specific components and weights shown in table 2.
Examples 15-16 hot dip galvanizing process for high strength fasteners, which differs from example 14 in the composition and weight of the acidic co-solvent included as specified in table 2.
Example 17 a hot dip galvanizing process for a high strength fastener comprising the specific components and weights shown in table 2, comprising the steps of:
s1, mixing and stirring sodium carbonate, zeolite powder, rice hull powder, tartaric acid, isooctyl alcohol polyoxyethylene ether and deionized water at the stirring speed of 1000r/min, and uniformly stirring to obtain the degreasing agent; mixing and stirring hydrochloric acid, sulfuric acid, polyglutamic acid, carboxyethyl sulfosuccinic acid and deionized water at the stirring speed of 900r/min, and uniformly stirring to obtain a pickling agent; mixing and stirring platycodon grandiflorum powder, hydroxypropyl methylcellulose, allyl alcohol polyoxyethylene polyoxypropylene ether, ammonium chloride, zinc chloride and deionized water at the stirring speed of 1000r/min, and uniformly stirring to obtain a plating assistant; mixing and stirring nitrate, nano aluminum sol, acidic cosolvent, honeysuckle extract, sodium dodecyl benzene sulfonate and deionized water at the stirring speed of 1100r/min, and uniformly stirring to obtain passivation solution;
s2, soaking the high-strength fastener in 6% sodium hydroxide solution at 30 ℃ for 5 min; then soaking the degreased high-strength fastener in the degreaser at 80 ℃ for 3min, and stirring at the stirring speed of 250r/min during the soaking process; after the first washing, immersing the fastener into a pickling agent for pickling, wherein the pickling temperature is 20 ℃, the pickling time is 10min, and after the second washing, obtaining a pretreated high-strength fastener;
s3, dipping the pre-treated high-strength fastener in a plating assistant agent, controlling the temperature at 40 ℃ and the dipping time for 90S, and obtaining the plated high-strength fastener after dipping;
s4, drying the assistant-plated high-strength fastener, immersing the assistant-plated high-strength fastener in zinc liquid, controlling the temperature of the zinc liquid to be 470 ℃ and the immersion time of the assistant-plated high-strength fastener in the zinc liquid to be 300S, extracting the immersed high-strength fastener from the plating solution at the extraction speed of 2m/min to obtain the galvanized high-strength fastener;
s5, cooling the galvanized high-strength fastener to 20 ℃, immersing the galvanized high-strength fastener into passivation solution for 40S at 20 ℃, and washing for the third time to obtain the passivated high-strength fastener;
and S6, drying, inspecting and packaging the passivated high-strength fastener to obtain a high-strength fastener finished product.
Example 18 a hot dip galvanizing process for a high strength fastener, differing from example 17 in the specific components and their weights included, as shown in table 2.
TABLE 2 Components and weights of examples 1-6, examples 9-10, and examples 13-18
Figure BDA0002994986030000081
Comparative example
Comparative example 1a hot galvanizing process for a high-strength fastener, which is different from example 1 in that the same amount of deionized water is used to replace platycodon grandiflorum powder in a plating assistant agent.
Comparative example 2 a hot dip galvanizing process for a high strength fastener was distinguished from example 1 in that an equal amount of deionized water was used in place of hydroxypropyl methylcellulose in the plating aid.
Comparative example 3 a hot galvanizing process for a high-strength fastener, which is different from example 1 in that the same amount of deionized water is used to replace platycodon root powder and hydroxypropyl methyl cellulose in the plating assistant.
Comparative example 4 a hot galvanizing process for a high strength fastener was distinguished from example 1 in that the immersion time in the plating aid was 20 seconds.
Comparative example 5 a hot galvanizing process for a high-strength fastener, which is different from example 1, the high-strength fastener is directly cooled to 20 c without being immersed in a passivation solution in step S4.
Comparative example 6 a hot galvanizing process for a high strength fastener consisting of the following components:
first step, deoiling: pouring the workpiece into a mixed solution of 10g/L sodium carbonate and 12g/L sodium hydroxide, wherein the temperature of the solution is 100 ℃, and the workpiece is completely soaked;
secondly, pickling, namely pickling the workpiece in a sulfuric acid solution with the concentration of 20% for 5min at the pickling temperature of 50 ℃, and washing the workpiece for 2min with clean water after pickling;
thirdly, cleaning the workpiece by using warm water at 60 ℃;
fourthly, dipping the plating assistant solution, namely putting the workpiece into zinc chloride-ammonium chloride aqueous solution for dipping at the dipping temperature of 60 ℃ for 3 min;
fifthly, drying and preheating, wherein the preheating temperature is 12 ℃, and the preheating time is 10 min;
sixthly, hot dip galvanizing, namely putting the preheated workpiece into zinc liquid, wherein the temperature of the zinc liquid is 495 ℃, the zinc dipping time is 3min, and a dust scraper removes floated zinc ash;
and step seven, cooling, namely putting the workpiece into cooling water at the temperature of 25 ℃ for cooling, then passivating and rinsing, putting the workpiece into passivation solution for passivating and rinsing, and then air-drying, wherein the passivation solution consists of titanate, phosphate, organic silicon modified epoxy resin, citric acid and water.
The sodium carbonate is selected from Cangzhou Lingang coastal chemical Co., Ltd; sodium hydroxide was obtained from jinan zhongjie chemical ltd; sulfuric acid from Suzhou Shashangyi electronics materials, Inc.; the zinc chloride is from Hebeili Hua Biotechnology GmbH, and the ammonium chloride is from Jinan Chengxuan chemical GmbH; titanate is from Ghan scientific & specialty Biotechnology Limited, model number specification is 17927-72-9; the phosphate is from Gentle Hongrun Biotech limited, cat # 146898790; the organic silicon modified epoxy resin is from New Gao and building materials Co., Ltd of Guangxi, and the product number is GH; citric acid is from Oufu Biotech, Inc., Jiangsu, under the product number SD-0002.
Steel washers were selected for the high strength fasteners of examples 1-18 and comparative examples 1-6.
Detection method
Experiment one: wear resistance test of plating layer
Experimental samples: galvanized steel gaskets were prepared by the processes of examples 1-18 and comparative examples 1-6, and the galvanized steel gaskets obtained from examples 1-18 were respectively designated as experimental samples 1-18, and the galvanized steel gaskets obtained from comparative examples 1-6 were respectively designated as comparative samples 1-6, and 5 were provided for each of experimental samples 1-18 and comparative samples 1-6.
An experimental instrument: a friction experiment machine (the brand is Shenzhen Fangyou science and technology Limited, the model is ABR-007); analytical balance (Brand of Mettler-Torledo International Inc., model XPR 204S/AC).
The experimental method comprises the following steps:
(1) the test sample 1 was weighed using an analytical balance to obtain m1Fixing the experimental sample 1 on a clamp of a friction experiment machine, and fixing a rubber for friction;
(2) and pre-rubbing, namely starting the machine for rubbing for three times, observing whether the rubbed area is proper or not and whether the experimental sample 1 is displaced or not, and adjusting the rubbing head and the experimental sample to proper positions.
(3) A175 g weight load was applied to the upper part of the rubbing head, and the surface of the rubbed area of the test specimen 1 was wiped for 50 times with a stroke of 20 mm.
(4) After the experiment is finished, weighing the experimental sample 1 to obtain m2(ii) a The degree of surface wear of the test sample 1 was observed, and the wear rate of the test sample 1 was calculated as (m)1-m2)/m1X 100%, the wear rates of 5 steel washers of the experimental sample 1 were obtained, and the average value of the wear rates was taken as the final wear rate of the experimental sample 1.
The experimental samples 2 to 18 and the comparative samples 1 to 6 were subjected to the experimental test of the wear resistance of the plating layer and the calculation of the wear rate according to the above experimental method.
The experimental results are as follows: the results of the wear rate tests for the experimental samples 1-18 and the comparative samples 1-6 are shown in Table 4.
Experiment two: test of scratch resistance of plating layer
Experimental samples: galvanized steel gaskets were prepared by the processes of examples 1-18 and comparative examples 1-6, and the galvanized steel gaskets obtained from examples 1-18 were respectively designated as experimental samples 1-18, and the galvanized steel gaskets obtained from comparative examples 1-6 were respectively designated as comparative samples 1-6, and 5 were provided for each of experimental samples 1-18 and comparative samples 1-6.
An experimental instrument: the brush is composed of a soft brush (Yulong brush product of Dongguan city, Inc.), a pressure-sensitive adhesive (Qingdao mountain eagle plastic, Inc.), and a blade (model Q12Y, mechanical die of Maanshan Kongfeng, Inc.).
The experimental method comprises the following steps: the anti-scratching performance of the plating layers of the experimental samples 1-18 and the comparative samples 1-6 is carried out by referring to the marking test of the colored paint and the varnish paint film of national standard GB/T9286-1998 and rating; for example, the scratch degree of the surfaces of 5 experimental samples 1 is observed, each experimental sample 1 is graded, and then the average value of the grading scores of the 5 experimental samples 1 is taken as the final scratch resistance grade of the experimental sample 1; the specific rating results are shown in table 3.
TABLE 3 rating standards
Figure BDA0002994986030000101
Figure BDA0002994986030000111
The plating scratch resistance tests were performed on the experimental samples 2 to 18 and the comparative samples 1 to 6 according to the above-described experimental methods.
The experimental results are as follows: the results of the test for the scratch resistance of the plating layers of the experimental samples 1 to 18 and the comparative samples 1 to 6 are shown in Table 4.
TABLE 4 results of the experiments of the experimental samples 1 to 18 and the comparative samples 1 to 6
Figure BDA0002994986030000112
As can be seen from the experimental data in Table 4, the wear rates of the experimental samples 1-18 were 2.21-3.01%, and the scratch resistance ratings were 0-2; the comparative samples 1-6 had a wear rate of 3.31-4.34% and a scratch resistance rating of 2-3; the experimental samples 1-18 have lower wear rates and better scratch resistance than the comparative samples 1-6, indicating that the galvanized steel gaskets prepared by the processes of examples 1-18 have better wear resistance.
It can be known from comparison experiment sample 1 and comparison sample 1-3, after adding balloonflower root powder and hydroxypropyl methylcellulose in the plating assistant agent, the wear rate reduces, the anti performance grade of drawing improves, show that balloonflower root powder and hydroxypropyl methylcellulose can strengthen the wear resistance of high strength fastener galvanizing coat, after saponin and hydroxypropyl methylcellulose combined action that contain in the balloonflower root powder, through reducing surface tension in the zinc liquid, effectively get rid of impurity such as molysite on surface, improve the cladding quality, strengthen the adhesive force of galvanizing coat and high strength fastener, thereby obtain the galvanizing coat that the wearability is good. Comparing the experimental sample 1 with the comparative sample 4, the plating quality is improved by controlling the plating assisting time within a proper range; comparing the experimental sample 1 and the comparative sample 5, it can be known that the high-strength fastener is effectively passivated by the passivation solution, and the corrosion resistance and the wear resistance of the zinc coating of the high-strength fastener are enhanced.
Comparing the experiment sample 1 with the experiment samples 3-4, the adhesive force between the high-strength fastener and the zinc liquid is enhanced after the high-strength fastener is soaked in the sodium hydroxide solution, so that the wear resistance of the zinc coating of the high-strength fastener is enhanced; comparing the experimental samples 4-6, it can be known that after the rice hull powder and the zeolite powder are added into the degreasing agent, the degreasing agent is matched with substances such as sodium hydroxide and the like to remove impurities such as grease on the surface of the high-strength fastener, and the removed grease is prevented from being attached to the surface of the high-strength fastener again, so that the adhesive force between the high-strength fastener and the zinc liquid is enhanced, and the wear resistance is enhanced; comparing the experiment sample 4 with the experiment samples 7-8, the degreasing agent is stirred, and the stirring speed is controlled, so that the wear resistance of the zinc coating of the high-strength fastener can be enhanced; probably because the stirring back, degreasing agent and high strength fastener surface fully contact, degreasing agent softens wetly to the impurity such as grease on high strength fastener surface fast, gets rid of impurity such as grease on high strength fastener surface, prevents simultaneously that impurity such as grease that gets rid of from adhering to on high strength fastener surface again for when the later stage helps plating and galvanize high strength fastener, strengthen the cohesion between molten zinc and the high strength fastener, strengthen the wear resistance on high strength fastener surface galvanizing coat.
Comparing the experiment sample 1 with the experiment samples 9-10, the wear resistance of the zinc coating of the high-strength fastener is enhanced after the polyglutamic acid is added into the pickling agent; the polyglutamic acid is a compound obtained by replacing hydrogen atoms on carbon atoms of carboxylic acid with amino groups, amino acid molecules contain two functional groups of amino groups and carboxyl groups, and metal ions in grease are chelated and adsorbed, so that the grease is removed, impurities are prevented from being adhered to the surface of the high-strength fastener again, and the wear resistance of a zinc coating of the high-strength fastener is enhanced; comparing the experimental sample 1 with the experimental samples 11-12, it can be known that a uniform zinc coating is formed on the surface of the high-strength fastener by controlling the lifting speed, so that the surface quality is improved, the wear resistance of the zinc coating on the surface of the high-strength fastener is enhanced, and the cost is saved; comparing the experimental sample 1 with the experimental samples 13-14, it can be seen that the honeysuckle extract in the passivation solution, after being combined with the nano alumina sol, promotes the surface of the zinc coating to form a layer of dense passivation film with good coverage and strong adhesion, thereby enhancing the corrosion resistance and wear resistance of the high-strength fastener; comparing the experimental samples 14-16, it can be seen that the acidic cosolvent is preferably citric acid and acetic acid, and forms nitric acid by combining with nitrate in the passivation solution and the nano alumina sol, so as to passivate the zinc coating on the surface of the high-strength fastener, and enhance the corrosion resistance and wear resistance of the zinc coating on the surface of the high-strength fastener; comparing the experimental sample 1 and the experimental samples 17 to 18, it can be seen that the degreasing agent, the pickling agent, the plating assistant agent and the passivation solution are preferably added and stirred, preferably at a higher speed, so as to enhance the wear resistance of the zinc coating of the high-strength fastener.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (8)

1. A hot galvanizing process of a high-strength fastener is characterized by comprising the following steps:
s1, degreasing the high-strength fastener, washing with water for the first time, pickling, washing with water for the second time to obtain a pretreated high-strength fastener;
s2, dipping the pre-treated high-strength fastener in a plating assistant agent, controlling the temperature to be 40-55 ℃ and the dipping time to be 30-90S, and obtaining the plated high-strength fastener after dipping;
s3, drying the plating-assisted high-strength fastener, immersing the fastener in zinc liquid, controlling the temperature of the zinc liquid at 420-;
s4, cooling the galvanized high-strength fastener to 20-40 ℃, immersing the galvanized high-strength fastener into passivation solution for 10-40S at 20-35 ℃, and washing for the third time to obtain the passivated high-strength fastener;
s5, drying, inspecting and packaging the passivated high-strength fastener to obtain a high-strength fastener finished product;
the plating assistant agent comprises the following raw materials in percentage by weight:
0.5 to 1.5 percent of platycodon grandiflorum powder;
0.1 to 1 percent of hydroxypropyl methyl cellulose;
0.2 to 0.8 percent of allyl alcohol polyoxyethylene polyoxypropylene ether;
8-20% of zinc chloride;
6-15% of ammonium chloride;
the balance of deionized water.
2. The hot galvanizing process for the high-strength fastener according to claim 1, wherein the degreasing in the step S1 includes the following steps:
a1, soaking the high-strength fastener in 3-6% sodium hydroxide solution at 30-50 deg.C for 3-5 min;
a2, soaking the high-strength fastener obtained in the step A1 in the degreasing agent at 70-80 ℃ for 3-5 min.
3. The hot galvanizing process for high-strength fasteners according to claim 2, wherein the degreasing agent in the step A2 is composed of the following raw materials in percentage by weight:
3-6% of rice hull powder;
0.5 to 2 percent of sodium carbonate;
zeolite powder 0.5-1.5%;
tartaric acid 0.1-0.4%;
1-3% of isooctyl alcohol polyoxyethylene ether;
the balance of deionized water.
4. The hot galvanizing process for high-strength fasteners according to claim 2, wherein in the step A2, the high-strength fasteners are stirred while being immersed in the degreasing agent, and the stirring speed is 100-400 r/min.
5. The hot galvanizing process of the high-strength fastener according to claim 1, wherein the pickling in the step S1 comprises the following specific steps: soaking the high-strength fastener after the first washing in a pickling agent for pickling, wherein the pickling temperature is 20-35 ℃, and the pickling time is 5-10 min; the pickling agent is prepared from the following raw materials in percentage by weight:
25-35% of hydrochloric acid;
3-6% of sulfuric acid;
0.4 to 0.8 percent of carboxyethyl sulfosuccinate;
1-3% of polyglutamic acid;
the balance of deionized water.
6. The hot galvanizing process for the high-strength fastener according to claim 1, wherein the dipped high-strength fastener is lifted out of the plating solution in step S3, and the lifting speed of the high-strength fastener is controlled to be 1-2.5 m/min.
7. The hot galvanizing process for the high-strength fastener according to claim 1, wherein the passivation solution is composed of the following raw materials in percentage by weight:
2-6% of nitrate;
1-4% of nano aluminum sol;
3-10% of acid cosolvent;
0.5-2% of honeysuckle extract;
0.2 to 0.8 percent of sodium dodecyl benzene sulfonate;
the balance of deionized water.
8. The hot galvanizing process for the high-strength fastener according to claim 7, wherein the acidic cosolvent comprises at least one of citric acid and acetic acid.
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