CN112412943B - Corrosion-resistant bolt and production process thereof - Google Patents

Corrosion-resistant bolt and production process thereof Download PDF

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Publication number
CN112412943B
CN112412943B CN202011295016.1A CN202011295016A CN112412943B CN 112412943 B CN112412943 B CN 112412943B CN 202011295016 A CN202011295016 A CN 202011295016A CN 112412943 B CN112412943 B CN 112412943B
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corrosion
bolt
resistant
parts
percent
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CN112412943A (en
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徐顺伦
徐祥淼
徐祥东
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Yueqing Xutai Screw Factory
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Yueqing Xutai Screw Factory
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B33/00—Features common to bolt and nut
    • F16B33/008—Corrosion preventing means
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/007—Heat treatment of ferrous alloys containing Co
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0093—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for screws; for bolts
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B33/00—Features common to bolt and nut
    • F16B33/06—Surface treatment of parts furnished with screw-thread, e.g. for preventing seizure or fretting
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The application relates to the field of bolts, and particularly discloses a corrosion-resistant bolt and a production process thereof. The corrosion-resistant bolt comprises a bolt body, wherein a corrosion-resistant coating covers the surface of the bolt body, and the corrosion-resistant coating is prepared from a complex containing boron trifluoride and 3-chloro-5-bromoanisole, a water-based acrylic resin emulsion, zinc borate, antimony oxide, N-bis-hydroxyethyl dodecyl amide, zinc sulfate, mica powder, heavy calcium carbonate and polyethylene glycol 200. The production process of the corrosion-resistant bolt comprises the following steps: step 1, directly contacting the bolt body with flame, heating, and then moving away from the flame to obtain a quenched bolt body; and 2, spraying the corrosion-resistant coating on the surface of the quenched bolt body, and then putting the bolt body into an oven to obtain the corrosion-resistant bolt. The corrosion-resistant bolt has good corrosion resistance, and meanwhile, the corrosion-resistant coating has strong binding capacity with the surface of the bolt body and is not easy to fall off.

Description

Corrosion-resistant bolt and production process thereof
Technical Field
The application relates to the field of bolts, in particular to a corrosion-resistant bolt and a production process thereof.
Background
The bolt is used as an essential accessory in industrial production and manufacturing, and is widely applied to electronic products, mechanical products, digital products, electrical equipment, electromechanical products and the like. In some occasions with complex environments and high sealing requirements, the corrosion resistance of the bolt is required to be high, the bolt is also commonly used for vehicles such as automobiles and high-speed rails, the vehicles are usually in open environments when in use, the bolt is easy to contact with rainwater, so that the bolt is rusted or corroded, the rusted or corroded bolt is easy to break, and potential safety hazards exist when the vehicles are used.
The surface of the bolt is usually covered with a layer of coating to prevent the bolt from rusting and corroding, but after the bolt is used for a long time, the coating is easy to age and wear, and after the coating ages, the binding capacity with the surface of the bolt is weakened to enable the coating to fall off, so that the corrosion resistance of the bolt is influenced.
Disclosure of Invention
In order to improve the binding capacity of the surface of the bolt and the corrosion-resistant coating, the application provides a corrosion-resistant bolt and a production process thereof.
In a first aspect, the present application provides a corrosion-resistant bolt, which adopts the following technical scheme:
the corrosion-resistant bolt comprises a bolt body, wherein the surface of the bolt body is covered with corrosion-resistant paint, and the bolt body is made of the following raw materials in percentage by weight: 0.2 to 0.5 percent of C, 0.15 to 0.23 percent of Si, 0.05 to 0.15 percent of Mn, 0.02 to 0.04 percent of P, 0.02 to 0.04 percent of S, 0.1 to 0.14 percent of Cu, 0.24 to 0.32 percent of Co0.08 to 0.24 percent of Al, 0.12 to 0.26 percent of Ti, 0.08 to 0.12 percent of Mo0.12 percent of V, 0.1 to 0.15 percent of Sc0.06 to 0.14 percent of Sc0.04 to 0.1 percent of Cr0.04, 0.12 to 0.26 percent of Tl, 0.16 to 0.34 percent of Hf0.16, and the balance of Fe and impurity elements;
the corrosion-resistant coating is prepared from the following raw materials in parts by weight: 8-16 parts of complex of boron trifluoride and 3-chloro-5-bromoanisole, 50-55 parts of aqueous acrylic resin emulsion, 1-2 parts of zinc borate, 3-7 parts of antimony oxide, 2-3 parts of N, N-bis-hydroxyethyl dodecyl amide, 1-3 parts of zinc sulfate, 15-20 parts of mica powder, 15-18 parts of heavy calcium carbonate and 1-5 parts of polyethylene glycol 200.
By adopting the technical scheme, the high-content Tl and Hf is added into the manufacturing material of the bolt body, so that the strength of the bolt body can be improved, the hardness of the bolt body can be improved, the corrosion resistance of the bolt body can be enhanced, and other properties can be realized; the surface of the bolt is coated with a corrosion-resistant coating containing a complex of boron trifluoride and 3-chloro-5-bromoanisole, and the corrosion-resistant coating isolates the bolt body from air and rainwater, so that the bolt has better corrosion resistance.
The complex of boron trifluoride and 3-chloro-5-bromoanisole can cover the surface of the bolt body, so that the corrosion resistance of the bolt is improved; meanwhile, a complex of boron trifluoride and 3-chloro-5-bromoanisole contains a chlorine group and a bromine group, the chlorine group and the bromine group have good electron withdrawing capability, the complex is easy to form a coordination bond with metal on the surface of the bolt body, Hf has good electron supplying capability, and the chlorine group, the bromine group and Hf have strong binding capability, so that the coating is tightly bound with the surface of the bolt body.
Antimony oxide, zinc borate, zinc sulfate, mica powder and heavy calcium carbonate can form gel in a system of polyethylene glycol 200 and aqueous acrylic resin emulsion by grafting with N, N-bis-hydroxyethyl dodecyl amide, so that the corrosion-resistant coating has better viscosity and chemical stability, and the binding capacity of the corrosion-resistant coating and the surface of the bolt body is improved.
Optionally, the corrosion-resistant coating also comprises 1-2 parts of Tl powder and 1-2 parts of Zr powder by weight.
By adopting the technical scheme, Tl powder, namely thallium powder, and Zr powder, namely zirconium powder, are also added into the corrosion-resistant coating, and Tl and Zr both have good hardness, so that the hardness of the corrosion-resistant coating is improved, and the wear resistance of the bolt is improved; meanwhile, the Zr and the Hf have similar chemical properties, and the Zr and the Hf have better binding capacity and compatibility, so that the binding capacity of the coating and the surface of the bolt body is improved.
Optionally, the preparation method of the complex of boron trifluoride and 3-chloro-5-bromoanisole is as follows:
simultaneously introducing boron trifluoride gas and 3-chloro-5-bromoanisole liquid into a closed reaction tank filled with nitrogen, wherein the volume ratio of the boron trifluoride gas to the 3-chloro-5-bromoanisole liquid is 4: 1, continuing to react for 12-15h after the introduction is finished, wherein the pressure in the reaction tank is 0.1-0.2MPa, and the reaction temperature is 50-60 ℃, thus obtaining the complex of boron trifluoride and 3-chloro-5-bromoanisole.
By the technical scheme, the complex of boron trifluoride and 3-chloro-5-bromoanisole is obtained.
Optionally, the 3-chloro-5-bromoanisole is dried, and the drying method is as follows: putting 1-3 parts by weight of anhydrous sodium sulfate into 10-13 parts by weight of 3-chloro-5-bromoanisole, and performing suction filtration to obtain dried 3-chloro-5-bromoanisole.
Through the technical scheme, boron trifluoride is easy to hydrolyze in the presence of moisture, the complex reaction of boron trifluoride and 3-chloro-5-bromoanisole is influenced, and the 3-chloro-5-bromoanisole is dried by using anhydrous sodium sulfate, so that the complex reaction effect of boron trifluoride and 3-chloro-5-bromoanisole is better.
Optionally, the preparation method of the corrosion-resistant coating comprises the following steps:
step 1, weighing a complex of boron trifluoride and 3-chloro-5-bromoanisole, zinc borate, antimony oxide, N-bis-hydroxyethyl dodecyl amide, zinc sulfate, mica powder, heavy calcium carbonate and polyethylene glycol 200 according to the required weight parts of a formula, and uniformly stirring and mixing to obtain a mixture;
and 2, adding the aqueous acrylic resin emulsion into the mixture, and stirring for 0.5-1h to obtain the corrosion-resistant coating.
By the technical scheme, the corrosion-resistant coating is obtained.
Optionally, the corrosion-resistant coating is adjusted to a pH of 4-5.5 with a pH adjuster.
By adopting the scheme, when the pH value of the corrosion-resistant coating is 4-5.5, the binding capacity of the complex of boron trifluoride and 3-chloro-5-bromoanisole and the surface of the bolt body is stronger, and the coating is not easy to fall off from the surface of the bolt body; meanwhile, the complex of boron trifluoride and 3-chloro-5-bromoanisole has good stability under an acidic condition, and the coating is not easy to decompose after wrapping the bolt, so that the coating has high compactness and long retention time, and the corrosion resistance and the durability of the corrosion resistance of the bolt are improved.
Optionally, the pH adjusting agent is phosphoric acid.
By adopting the technical scheme, the phosphoric acid is not easy to volatilize and decompose, has poor oxidability and good stability, is not easy to generate oxidation reduction reaction with Zr and Tl, and can keep the original metal properties of the Zr and the Tl while adjusting the pH.
In a second aspect, the present application provides a production process of a corrosion-resistant bolt, which adopts the following technical scheme:
a production process of a corrosion-resistant bolt comprises the following steps:
step 1, directly contacting the bolt body with flame, heating to 100-;
and 2, immediately spraying the corrosion-resistant coating on the surface of the quenched bolt body, and then putting the bolt body into a drying oven at the temperature of 40-50 ℃ for 4-5 hours to obtain the corrosion-resistant bolt.
By adopting the technical scheme, the quenching can remove dust and stains on the surface of the bolt body, so that the dust and the stains are not easy to influence the binding capacity of the coating and the surface of the bolt, meanwhile, the quenching can heat the surface of the bolt, the corrosion-resistant coating is sprayed on the heated surface of the bolt, the flowability of the coating on the surface of the bolt body is better, the coating is uniformly covered, and a film formed by the coating is more compact.
In summary, the present application has the following beneficial effects:
1. the complex of boron trifluoride and 3-chloro-5-bromoanisole is added into the manufacturing material of the corrosion-resistant coating, so that the coating is more tightly combined with the surface of the bolt body.
2. Zr powder and Tl powder are added into the corrosion-resistant coating, so that a protective film formed by the corrosion-resistant coating has higher hardness.
3. The pH value of the corrosion-resistant coating is adjusted to 4-5.5, so that the corrosion resistance of the coating is better, and the binding capacity of the coating and the surface of the bolt under an acidic condition is further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The water-based acrylic resin emulsion is water-based acrylic resin emulsion R-20 sold by pure whitening chemical industry Co., Ltd, Guangzhou city; the polyethylene glycol 200 is sold by a Haian petrochemical plant in Jiangsu province; n, N-bis-hydroxyethyl-dodecyl-amide is sold by Nantong Xitai chemical Co., Ltd., and is in the type of CD-110.
Example 1:
the corrosion-resistant bolt comprises a bolt body, wherein the bolt body is made of the following raw materials in percentage by weight: 0.2% of C, 0.15% of Si, 0.05% of Mn0.05%, 0.02% of P, 0.02% of S, 0.1% of Cu0.24%, 0.24% of Co0.08% of Al, 0.12% of Ti0.08%, 0.08% of Mo0.1%, 0.06% of Sc0.06%, 0.04% of Cr0.04%, 0.12% of Tl, 0.16% of Hf0, and the balance of Fe and impurity elements, wherein the bolt body is formed by cutting an alloy containing formula elements, and then performing cold heading, thread rolling and heat treatment processes.
The preparation method of the complex of boron trifluoride and 3-chloro-5-bromoanisole comprises the following steps:
introducing boron trifluoride gas and 3-chloro-5-bromoanisole liquid into a closed reaction tank filled with nitrogen at the same time, wherein the volume ratio of the boron trifluoride gas to the 3-chloro-5-bromoanisole liquid is 4: 1, the flow rate of boron trifluoride gas when introduced into the reaction tank was 0.5X10-3m3Flow rate of the/s, 3-chloro-5-bromoanisole liquid was 0.2X10-3m3And/s, continuing to react for 12 hours after the introduction is finished, wherein the pressure in the reaction tank is 0.1MPa, and the reaction temperature is 50 ℃, so as to obtain the complex of boron trifluoride and 3-chloro-5-bromoanisole.
The surface of the bolt body is covered with corrosion-resistant paint, and the preparation method of the corrosion-resistant paint comprises the following steps:
step 1, weighing 8 parts by weight of a complex of boron trifluoride and 3-chloro-5-bromoanisole, 1 part by weight of zinc borate, 3 parts by weight of antimony oxide, 2 parts by weight of N, N-bis-hydroxyethyl dodecylamide, 1 part by weight of zinc sulfate, 15 parts by weight of mica powder, 15 parts by weight of heavy calcium carbonate and 1 part by weight of polyethylene glycol 200, and uniformly stirring and mixing to obtain a mixture;
and 2, adding 50 parts of aqueous acrylic emulsion into the mixture, stirring for 0.5h, and adjusting the pH to 6.3 by using phosphoric acid to obtain the corrosion-resistant coating.
The production process of the corrosion-resistant bolt comprises the following steps:
step 1, directly contacting the bolt body with flame, heating to 100 ℃, removing the flame, and cooling to 50 ℃ of the surface temperature of the bolt body to obtain a quenched bolt body;
and 2, immediately spraying the corrosion-resistant coating on the surface of the quenched bolt body, and then putting the bolt body into an oven at 40 ℃ for 4 hours to obtain the corrosion-resistant bolt.
Example 2:
the corrosion-resistant bolt comprises a bolt body, wherein the bolt body is made of the following raw materials in percentage by weight: 0.5% of C, 0.23% of Si, 0.15% of Mn0.04% of P, 0.04% of S, 0.14% of Cu0.32% of Co0.24% of Al, 0.26% of Ti0.12% of Mo0.12% of V, 0.15% of Sc0.14% of Cr0.1%, 0.26% of Tl, 0.34% of Hf0.34% of the balance of iron and impurity elements, and the bolt body is formed by cutting an alloy containing the formula elements and then performing cold heading, thread rolling and heat treatment processes.
The preparation method of the complex of boron trifluoride and 3-chloro-5-bromoanisole comprises the following steps:
introducing boron trifluoride gas and 3-chloro-5-bromoanisole liquid into a closed reaction tank filled with nitrogen at the same time, wherein the volume ratio of the boron trifluoride gas to the 3-chloro-5-bromoanisole liquid is 4: 1, flow rate of boron trifluoride gas was 0.5X10- 3m3Flow rate of the/s, 3-chloro-5-bromoanisole liquid was 0.2X10-3m3And/s, continuing to react for 15 hours after the introduction is finished, wherein the pressure in the reaction tank is 0.2MPa, and the reaction temperature is 60 ℃, so as to obtain the complex of boron trifluoride and 3-chloro-5-bromoanisole.
The surface of the bolt body is covered with corrosion-resistant paint, and the preparation method of the corrosion-resistant paint comprises the following steps:
step 1, weighing 16 parts by weight of a complex of boron trifluoride and 3-chloro-5-bromoanisole, 2 parts by weight of zinc borate, 7 parts by weight of antimony oxide, 3 parts by weight of N, N-bis-hydroxyethyl dodecylamide, 3 parts by weight of zinc sulfate, 20 parts by weight of mica powder, 18 parts by weight of heavy calcium carbonate and 5 parts by weight of polyethylene glycol 200, and uniformly stirring and mixing to obtain a mixture;
and 2, adding 55 parts of acrylic resin into the mixture, stirring for 1h, and adjusting the pH to 6.3 by using phosphoric acid to obtain the corrosion-resistant coating.
The production process of the corrosion-resistant bolt comprises the following steps:
step 1, directly contacting the bolt body with flame, heating to 150 ℃, removing the flame, and cooling to 70 ℃ of the surface temperature of the bolt body to obtain a quenched bolt body;
and 2, immediately spraying the corrosion-resistant coating on the surface of the quenched bolt body, and then putting the bolt body into a 50-DEG C oven for 5 hours to obtain the corrosion-resistant bolt.
Example 3:
the corrosion-resistant bolt comprises a bolt body, wherein the bolt body is made of the following raw materials in percentage by weight: 0.3% of C, 0.2% of Si, 0.1% of Mn0, 0.03% of P, 0.03% of S, 0.12% of Cu0.12%, 0.3% of Co0.12%, 0.12% of Al, 0.2% of Ti, 0.1% of Mo0.12%, 0.1% of V, 0.1% of Sc0.06% of Cr0.06%, 0.12-0.26% of Tl, 0.16-0.34% of Hf0.16, and the balance of iron and impurity elements, wherein the bolt body is formed by cutting an alloy containing formula elements and then performing cold heading, thread rolling and heat treatment processes.
The preparation method of the complex of boron trifluoride and 3-chloro-5-bromoanisole comprises the following steps:
introducing boron trifluoride gas and 3-chloro-5-bromoanisole liquid into a closed reaction tank filled with nitrogen at the same time, wherein the volume ratio of the boron trifluoride gas to the 3-chloro-5-bromoanisole liquid is 4: 1, flow rate of boron trifluoride gas was 0.5X10- 3m3Flow rate of the/s, 3-chloro-5-bromoanisole liquid was 0.2X10-3m3And/s, continuing to react for 13 hours after the introduction is finished, wherein the pressure in the reaction tank is 0.15MPa, and the reaction temperature is 55 ℃, so as to obtain the complex of boron trifluoride and 3-chloro-5-bromoanisole.
The surface of the bolt body is covered with corrosion-resistant paint, and the preparation method of the corrosion-resistant paint comprises the following steps:
step 1, weighing 11 parts by weight of a complex of boron trifluoride and 3-chloro-5-bromoanisole, 53 parts by weight of acrylic resin, 1 part by weight of zinc borate, 5 parts by weight of antimony oxide, 2 parts by weight of N, N-bis-hydroxyethyl dodecyl amide, 2 parts by weight of zinc sulfate, 17 parts by weight of mica powder, 16 parts by weight of heavy calcium carbonate and 3 parts by weight of polyethylene glycol 200, and uniformly stirring and mixing to obtain a mixture;
and 2, adding acrylic resin into the mixture, stirring for 0.8h, and adjusting the pH to 6.3 by using phosphoric acid to obtain the corrosion-resistant coating.
The production process of the corrosion-resistant bolt comprises the following steps:
step 1, directly contacting the bolt body with flame, heating to 130 ℃, removing the flame, and cooling to 60 ℃ of the surface temperature of the bolt body to obtain a quenched bolt body;
and 2, immediately spraying the corrosion-resistant coating on the surface of the quenched bolt body, and then putting the bolt body into a 45-DEG C oven for 4.5 hours to obtain the corrosion-resistant bolt.
Example 4:
the difference from example 3 is that 1 part by weight of Tl powder and 1 part by weight of Zr powder were added in step 1 of the method for preparing the corrosion resistant coating.
Example 5:
the difference from the example 3 is that the 3-chloro-5-bromoanisole is dried by the following method:
and (3) putting 3 parts by weight of anhydrous sodium sulfate into 13 parts by weight of 3-chloro-5-bromoanisole, and performing suction filtration to obtain dried 3-chloro-5-bromoanisole.
Example 6:
the difference from example 3 is that the corrosion resistant coating is adjusted to a pH of 4 with phosphoric acid.
Example 7:
the difference from example 3 is that the corrosion-resistant coating is adjusted to a pH of 5.5 with phosphoric acid.
Example 8:
the difference from example 3 is that the corrosion-resistant coating is adjusted to a pH of 5 with phosphoric acid.
Comparative example 1:
the difference from example 3 is that the bolt body surface is not covered with the corrosion-resistant coating.
Comparative example 2:
the difference from example 3 is that the corrosion-resistant coating does not contain a complex of boron trifluoride and 3-chloro-5-bromoanisole.
Comparative example 3:
the difference from example 3 is that Tl is not contained in the material for manufacturing the bolt body.
Comparative example 4:
the difference from example 3 is that Hf is not contained in the material for making the bolt body.
Comparative example 5:
the difference from example 3 is that Tl and Hf are not contained in the material for manufacturing the bolt body.
Comparative example 6:
the difference from the example 3 is that in the step 2 of the production process of the corrosion-resistant bolt, the surface temperature of the bolt is 45 ℃ when the coating is sprayed.
Comparative example 7:
the difference from the example 3 is that in the step 2 of the production process of the corrosion-resistant bolt, the surface temperature of the bolt is 80 ℃ when the coating is sprayed.
Performance test
Salt spray corrosion test:
the corrosion-resistant bolts of the examples and comparative examples were tested with reference to GB/T10125-2012 "salt spray test for artificial atmosphere corrosion experiments". And performing a salt spray test on the corrosion-resistant bolt by using an acetic acid solution with the mass percent of 6%, and observing the corrosion-resistant bolt after 500h, 800h, 900h and 1000h of the salt spray test.
And (3) testing the binding capacity:
the following test methods were used to determine the bond strength of the anticorrosive coating to the surface of the corrosion-resistant bolt: the alloy materials used for manufacturing the bolts in the examples 1 to 8 and the comparative examples 1 to 7 are made into a wafer with the diameter of 20mm and the thickness of 2mm, and then the corrosion-resistant coating treatment is carried out by adopting the same process to obtain a test sample to be tested. The test specimens to be tested are tested for their bond strength with reference to GB/T5210-2006 adhesion test by the paint and varnish pull-open method. The test was carried out by using an AGS-J tensile testing machine sold by Shimadzu corporation, hong Kong, at a tensile speed of 10mm/min, and the adhesive was ALTECO 110 type super glue.
TABLE 1
Salt spray test for 500h Salt spray test for 800h Salt spray test 900h Salt spray test for 1000h Bonding strength MPa
Example 1 No obvious effect No obvious effect Visible corrosion - 32
Example 2 No obvious effect No obvious effect Visible corrosion - 33
Example 3 No obvious effect No obvious effect Visible corrosion - 35
Example 4 No obvious effect No obvious effect No obvious effect Visible corrosion 42
Example 5 No obvious effect No obvious effect No obvious difference Visible corrosion 39
Example 6 No obvious difference No obvious effect No obvious effect No obvious difference 44
Example 7 No obvious effect No obvious effect No obvious effect No obvious difference 44
Example 8 No obvious effect No obvious difference No obvious effect No obvious effect 46
Comparative example 1 Visible corrosion - - - -
Comparative example 2 No obvious effect Visible corrosion - - 18
Comparative example 3 No obvious effect Visible corrosion - - 27
Comparative example 4 No obvious effect Visible corrosion - - 24
Comparative example 5 No obvious effect Visible corrosion - - 22
Comparative example 6 No obvious effect Visible corrosion - - 26
Comparative example 7 No obvious effect Visible corrosion - - 27
The following analyses were performed in conjunction with table 1:
combining examples 3 and 4 with table 1, it can be seen that the corrosion resistance of the corrosion resistant coating is enhanced by the addition of Tl powder and Zr powder.
By combining the example 3 and the example 5 and the table 1, it can be seen that after the 3-chloro-5-bromoanisole is dried, the atomization of boron trifluoride is reduced, that is, the waste of boron trifluoride in the reaction system is reduced, the complex reaction yield of boron trifluoride and 3-chloro-5-bromoanisole is high, the content of active ingredients in a complex of boron trifluoride and 3-chloro-5-bromoanisole is increased, the active ingredients in the corrosion-resistant coating are increased, and the corrosion resistance of the corrosion-resistant bolt is improved.
It can be seen from the combination of example 3 and examples 6 to 8 and table 1 that the pH of the corrosion-resistant coating is not adjusted, that is, the corrosion-resistant coating with pH 6.3 has a corrosion resistance lower than that of the corrosion-resistant coating with pH4 or 5 or 5.5, and the bonding strength is probably because the complex of boron trifluoride and 3-chloro-5-bromoanisole and the surface of the bolt body have better bonding ability under the condition of pH4-5.5, so that the bonding strength of the corrosion-resistant coating and the surface of the bolt is better, and the complex of boron trifluoride and 3-chloro-5-bromoanisole has better stability under the acidic condition, and the coating is not easily decomposed after wrapping the bolt, so that the compactness of the coating is high, the retention time is long, and the corrosion resistance and the durability of the corrosion resistance are improved.
Combining example 3 and comparative example 1 and table 1, it can be seen that the corrosion-resistant coating has a significant corrosion resistance, which can improve the corrosion resistance of the bolt.
It can be seen from the combination of example 3 and comparative examples 2 to 5 and table 1 that the corrosion resistance of the corrosion-resistant bolt is improved by adding Tl and Hf to the material of the bolt body. The complex of boron trifluoride and 3-chloro-5-bromoanisole has good corrosion resistance, and the complex of boron trifluoride and 3-chloro-5-bromoanisole has electron-withdrawing groups such as chlorine groups and bromine groups, so that coordination bonds can be easily formed with metal on the surface of the bolt body, and the binding force of the corrosion-resistant coating and the surface of the bolt is improved; the Hf and Tl have good electron supply capacity, the combination capacity of the chlorine group and the bromine group with the Hf is strong, and the combination strength of the corrosion-resistant coating and the surface of the bolt body can be obviously enhanced.
When the surface temperature of the bolt body is 50-70 ℃, the corrosion-resistant coating is sprayed on the surface of the bolt body, so that the produced corrosion-resistant bolt has better corrosion resistance, the flowing property of the coating is poorer due to lower temperature, the corrosion-resistant coating is not easy to uniformly cover the surface of the bolt, and the corrosion resistance and the bonding strength of the corrosion-resistant bolt are influenced; when the temperature is too high, the molecular structure of the complex of boron trifluoride and 3-chloro-5-bromoanisole can be damaged, and the corrosion resistance and the bonding strength of the corrosion-resistant coating are influenced.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.

Claims (8)

1. The corrosion-resistant bolt comprises a bolt body and is characterized in that corrosion-resistant paint covers the surface of the bolt body, and the bolt body is made of the following raw materials in percentage by weight: 0.2 to 0.5 percent of C, 0.15 to 0.23 percent of Si, 0.05 to 0.15 percent of Mn, 0.02 to 0.04 percent of P, 0.02 to 0.04 percent of S, 0.1 to 0.14 percent of Cu, 0.24 to 0.32 percent of Co0.08 to 0.24 percent of Al, 0.12 to 0.26 percent of Ti, 0.08 to 0.12 percent of Mo0.12 percent of V, 0.1 to 0.15 percent of Sc0.06 to 0.14 percent of Sc0.04 to 0.1 percent of Cr0.04, 0.12 to 0.26 percent of Tl, 0.16 to 0.34 percent of Hf0.16, and the balance of Fe and impurity elements;
the corrosion-resistant coating is prepared from the following raw materials in parts by weight: 8-16 parts of complex of boron trifluoride and 3-chloro-5-bromoanisole, 50-55 parts of aqueous acrylic resin emulsion, 1-2 parts of zinc borate, 3-7 parts of antimony oxide, 2-3 parts of N, N-bis-hydroxyethyl dodecyl amide, 1-3 parts of zinc sulfate, 15-20 parts of mica powder, 15-18 parts of heavy calcium carbonate and 1-5 parts of polyethylene glycol 200.
2. A corrosion resistant bolt according to claim 1 wherein: the corrosion-resistant coating also comprises 1-2 parts of Tl powder and 1-2 parts of Zr powder by weight.
3. A corrosion resistant bolt according to claim 1 wherein: the preparation method of the complex of boron trifluoride and 3-chloro-5-bromoanisole comprises the following steps:
introducing boron trifluoride gas and 3-chloro-5-bromoanisole liquid into a closed reaction tank filled with nitrogen at the same time, wherein the volume ratio of the boron trifluoride gas to the 3-chloro-5-bromoanisole liquid is 4: 1, continuing to react for 12-15h after the introduction is finished, wherein the pressure in the reaction tank is 0.1-0.2MPa, and the reaction temperature is 50-60 ℃, thus obtaining the complex of boron trifluoride and 3-chloro-5-bromoanisole.
4. A corrosion resistant bolt according to claim 3 wherein: the 3-chloro-5-bromoanisole is dried, and the drying method comprises the following steps: putting 1-3 parts by weight of anhydrous sodium sulfate into 10-13 parts by weight of 3-chloro-5-bromoanisole, and performing suction filtration to obtain dried 3-chloro-5-bromoanisole.
5. A corrosion resistant bolt according to claim 1 wherein: the preparation method of the corrosion-resistant coating comprises the following steps:
step 1, weighing a complex of boron trifluoride and 3-chloro-5-bromoanisole, zinc borate, antimony oxide, N-bis-hydroxyethyl dodecyl amide, zinc sulfate, mica powder, heavy calcium carbonate and polyethylene glycol 200 according to the required weight parts of a formula, and uniformly stirring and mixing to obtain a mixture;
and 2, adding the aqueous acrylic resin emulsion into the mixture, and stirring for 0.5-1h to obtain the corrosion-resistant coating.
6. A corrosion resistant bolt according to claim 5 wherein: the pH value of the corrosion-resistant coating is adjusted to 4-5.5 by using a pH regulator.
7. A corrosion resistant bolt according to claim 6 wherein: the pH regulator is phosphoric acid.
8. A process for the production of a corrosion resistant bolt according to any one of claims 1 to 7 comprising the steps of:
step 1, directly contacting the bolt body with flame, heating to 100-;
and 2, immediately spraying the corrosion-resistant coating on the surface of the quenched bolt body, and then putting the bolt body into a drying oven at the temperature of 40-50 ℃ for 4-5 hours to obtain the corrosion-resistant bolt.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5292055A (en) * 1976-01-29 1977-08-03 Kubota Ltd Preventive process against corrosion of bolt and nut
JPH02304209A (en) * 1989-05-16 1990-12-18 Kubota Corp Structure of corrosion-resistant bolt and nut
CN103382336A (en) * 2013-07-08 2013-11-06 吴江市物华五金制品有限公司 Flame-retardant anti-corrosion paint
CN104230972A (en) * 2014-08-16 2014-12-24 刘小秦 Method for purifying anisole-boron trifluoride complex
CN105177456A (en) * 2015-07-28 2015-12-23 宁波市镇海甬鼎紧固件制造有限公司 Corrosion-resistant bolt alloy material and manufacturing method of bolts
CN107879902A (en) * 2017-11-17 2018-04-06 陕西环珂生物科技有限公司 Utilize the method for methyl sodium sulphate synthesis methyl phenyl ethers anisole
CN209989290U (en) * 2019-03-20 2020-01-24 润泰化学南通有限公司 Boron trifluoride complex purification treatment device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5292055A (en) * 1976-01-29 1977-08-03 Kubota Ltd Preventive process against corrosion of bolt and nut
JPH02304209A (en) * 1989-05-16 1990-12-18 Kubota Corp Structure of corrosion-resistant bolt and nut
CN103382336A (en) * 2013-07-08 2013-11-06 吴江市物华五金制品有限公司 Flame-retardant anti-corrosion paint
CN104230972A (en) * 2014-08-16 2014-12-24 刘小秦 Method for purifying anisole-boron trifluoride complex
CN105177456A (en) * 2015-07-28 2015-12-23 宁波市镇海甬鼎紧固件制造有限公司 Corrosion-resistant bolt alloy material and manufacturing method of bolts
CN107879902A (en) * 2017-11-17 2018-04-06 陕西环珂生物科技有限公司 Utilize the method for methyl sodium sulphate synthesis methyl phenyl ethers anisole
CN209989290U (en) * 2019-03-20 2020-01-24 润泰化学南通有限公司 Boron trifluoride complex purification treatment device

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