CN114773937A - Phosphating-free plate based on endless rolling process and preparation method thereof - Google Patents

Phosphating-free plate based on endless rolling process and preparation method thereof Download PDF

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CN114773937A
CN114773937A CN202210709428.8A CN202210709428A CN114773937A CN 114773937 A CN114773937 A CN 114773937A CN 202210709428 A CN202210709428 A CN 202210709428A CN 114773937 A CN114773937 A CN 114773937A
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phosphating
substrate
parts
free
rolling process
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李华英
吴进
丁宁
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Taiyuan University of Science and Technology
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    • 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
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • 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
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention belongs to the field of metal materials, and particularly relates to a preparation method of a non-phosphating plate based on a headless rolling process, which comprises the following steps: adopting ultrathin hot-rolled strip steel produced by a headless rolling process as a substrate without phosphating treatment; removing an oxide layer of the substrate by a continuous pickling line, and then ensuring the cleanliness of the surface of the substrate through a rinsing process; preparing a metal surface treating agent; and coating the prepared metal surface treating agent on the surface of a substrate by a roller coating process, and drying to prepare the phosphating-free plate. The preparation method provided by the invention can save equipment, labor, time and environmental cost of a phosphating process, can provide the phosphating-free process steel coil meeting the requirements of environmental protection, energy conservation and low emission, is directly used by downstream customers, and solves the fundamental problem for industrial application, so that coating users can save relevant processes of alkali washing, neutralization, surface adjustment and phosphating, directly spray paint or plastic, and simultaneously eliminate environmental pollution of the users in a series of pretreatment processes.

Description

Phosphating-free plate based on endless rolling process and preparation method thereof
Technical Field
The invention belongs to the field of metal materials, particularly relates to a non-phosphatized plate based on a headless rolling process and a preparation method thereof, and particularly relates to a non-phosphatized plate which is environment-friendly, energy-saving and low-emission and can be directly used for painting or plastic spraying of coating downstream customers and a preparation method thereof.
Background
In industries such as electrical cabinets and the like, surface pretreatment is needed before plastic spraying or paint spraying to remove oil and coat a film to improve surface adhesion. Common processes are phosphating and shot blasting, wherein the phosphating process is most widely applied. The traditional phosphating process contains a plurality of heavy metal ions such as zinc, manganese, nickel and the like, has a large amount of phosphorus, is difficult to discharge and treat waste water, and can not meet the national environmental protection requirement on the coating industry. Meanwhile, a large amount of phosphorization slag is generated in the phosphorization treatment process, a corresponding slag removing device is needed, the phosphorization use temperature is 30-50 ℃, an auxiliary heating device and a heat source are needed for heating the phosphorization tank, a large amount of overflow water is needed for rinsing the workpiece after phosphorization, the production cost is high, and the environmental pollution is caused.
With the environmental protection of the state in recent years, the phosphorization process belongs to the high pollution industry and is monitored in an important way, forcing phosphorization customers to adopt the following process paths: (1) a large amount of environment-friendly equipment is purchased, so that the investment is huge and the operation cost is high; (2) adopting a galvanized plate; not only the cost per ton of steel is increased by 500 yuan or more, but also the bonding force of the coating is poor, the zinc layer affects the welding quality and causes zinc smoke pollution to harm the artificial health; (3) areas with low outsourcing environmental pressures will still be phosphated and will also have long transport periods and high costs.
Disclosure of Invention
In view of this, the invention aims to provide a method for preparing a phosphated-free plate based on a headless rolling process, and aims to solve the problem that coating users in the downstream industry encounter the problem of environmental protection and cost which are difficult to process in the traditional phosphated process.
Another objective of the present invention is to provide a phosphatization-free plate produced based on a endless rolling process, which aims to save equipment, labor, time and environmental protection cost of a work transfer phosphating process, and can directly provide a phosphatization-free steel coil for customers, so as to solve fundamental problems for industrial application.
In order to achieve the purpose of the invention, the technical scheme is as follows:
the preparation method of the phosphating-free plate based on the endless rolling process comprises the following steps:
(1) adopting 0.8-1.5mm ultrathin hot-rolled strip steel produced by a headless rolling process as a substrate without phosphating treatment;
(2) removing an oxide layer of the substrate by a continuous pickling line, and rinsing the substrate by deionized water to ensure the cleanliness of the surface of the substrate; wherein the technical indexes of the deionized water are as follows: electrical conductivity of<10 mu S/cm, pH value of 6-7, chloride ion less than or equal to 2.8mg/L and soluble SiO2≤0.2mg/L；
(3) Preparing a metal surface treating agent, wherein the metal surface treating agent is prepared from the following raw materials in parts by weight: 1-5 parts of a silane coupling agent; 1-5 parts of modified resin; 0.5-2.5 parts of hydrolysis stabilizer; 1.5-2.5 parts of curing agent and 10-25 parts of alcohol; 60-86 parts of deionized water, and is prepared by the following preparation method, wherein the preparation process is as follows: sequentially adding 10-25 parts of alcohol, 5-20 parts of deionized water and 0.5-2.5 parts of hydrolysis stabilizer into a preparation container, then adding 1-5 parts of silane coupling agent and 1-5 parts of modified resin into the preparation container under the condition of shearing and stirring, stirring and reacting for 1-3.5 hours at room temperature, after the stirring and reacting are finished, adding 1.5-2.5 parts of curing agent into the preparation container, uniformly stirring, and finally adding the rest deionized water into the preparation container to form the metal surface treating agent; wherein the deionized water used in the step (3) is the same as the deionized water used in the step (2);
(4) and (3) coating the metal surface treating agent prepared in the step (3) on the surface of the substrate rinsed in the step (2) through a roller coating process, and drying to prepare the phosphating-free plate, wherein the drying temperature is 200-350 ℃, the drying time is 2-10s, and the plate surface temperature of the phosphating-free plate out of a drying furnace is more than or equal to 50 ℃.
Further, the unevenness of the surface of the substrate is less than or equal to 15I, and the roughness Ra is: 0.5 to 2.0 μm.
Preferably, the silane coupling agent is one or more of methacryloxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, propyl trimethoxy silane, and propyl triethoxy silane.
Preferably, the modified resin is selected from one or more of modified acrylic resin, modified alkyd resin and modified polyester resin.
Preferably, the hydrolysis stabilizer is selected from one of nonionic acrylamide and fatty acid polyglycol ester.
Preferably, the curing agent is one of trioxymethylene and anhydrous ethylenediamine; the alcohol is selected from one or more of methanol, ethanol and propanol.
Preferably, the roller coating process adopts a forward coating or reverse coating mode, a metal surface treating agent is uniformly coated on the upper surface and the lower surface of a rinsed substrate to form a coating film, and the coating film is dried to form the phosphating-free plate, wherein the weight of a single-surface coating film in the phosphating-free plate is more than or equal to 0.3 g/square meter, and the film thickness of the coating film is 2 microns.
Further, the base plate enters a continuous pickling machine for pickling after uncoiling, laser welding and phosphorus breaking and straightening.
Further, the rinsed substrate is subjected to leveling process, then the metal surface treating agent is coated on the surface of the substrate through a roller coating process and then dried, and after drying is finished, coiling is carried out to form a phosphating-free steel coil for downstream users to use.
The invention also provides a phosphating-free plate produced based on the endless rolling process, and the phosphating-free plate is prepared based on the preparation method.
The invention has the beneficial effects that:
the preparation method of the phosphating-free plate based on the endless rolling process can save equipment, labor, time and environmental protection cost of a phosphating process, can provide a phosphating-free process steel coil which meets the requirements of environmental protection, energy conservation and low emission, is directly used by downstream customers, and can solve fundamental problems for industrial application; therefore, the coating user can save the related procedures of alkali washing, neutralization, surface adjustment and phosphating, directly carry out paint spraying or plastic spraying and also eliminate the environmental pollution of the user in a series of pretreatment procedures. In addition, the invention has the following advantages:
(1) the invention adopts the ultra-thin hot-rolled strip steel as the base plate without phosphating treatment, and realizes the aim of reducing the manufacturing cost by a mode of replacing cold by heat;
(2) the invention adopts the specially configured metal surface treating agent, and a silanized film with the thickness of 2 mu m can be formed on the phosphatization-free rolled plate after roller coating treatment, so that the phosphatization-free rolled plate has good heat resistance and acid and alkali resistance, the diffusion of internal pitting corrosion is inhibited, the electrochemical corrosion speed of external acid and alkali is relieved, and meanwhile, the steel rolled plate treated by the metal surface treating agent can meet the requirement of rust resistance under the condition that the phosphatization-free rolled plate is not coated with oil and also has the performance of the binding force of a coating layer of the traditional phosphatization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart of the present invention for producing a phosphating-free plate based on a endless rolling process;
FIG. 2 is a flow chart of the process for producing the substrate without phosphating treatment by the headless rolling process.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Due to the high quality requirements of the country on environmental protection in recent years, coating users are forced to change the traditional phosphating process or abandon the original phosphating process, and the requirements of the country on environmental protection, energy conservation and low emission can be met.
In this regard, downstream coating users are urgently in need of a treatment process and steel that meet the above-mentioned high-quality environmental requirements to solve the problems facing today. Thus, the present invention is applicable.
The invention adopts the ultra-thin hot-rolled strip steel as the base plate without phosphating treatment, and realizes the aim of reducing the manufacturing cost by a mode of replacing cold by heat; meanwhile, the invention adopts the specially configured metal surface treating agent, and a silanized film with the thickness of 2 microns can be formed on the phosphatization-free rolled plate after roller coating and drying treatment, so that the phosphatization-free rolled plate has good heat resistance, acid and alkali resistance, the diffusion of internal pitting corrosion is inhibited, the electrochemical corrosion speed of external acid and alkali is relieved, and meanwhile, the steel rolled plate treated by the metal surface treating agent can meet the requirement of the rust resistance of the phosphatization-free rolled plate under the condition of no oil coating and also has the performance of the binding force of a coating layer of the traditional phosphatization.
Before the technical solution of the present invention is explained in detail, a brief description of the endless rolling process according to the present invention will be given.
The endless rolling process is a technical breakthrough of the traditional hot rolling strip steel production, and refers to a technology that a rough-rolled plate blank is welded on a middle roller way and continuously passes through a finishing mill group. Compared with the traditional production mode, the process has the advantages that the links of threading and drifting of the strip steel in the finishing mill set are reduced, and the strip steel is rolled under the condition of constant tension, so that the ratio of the head and the tail of the strip steel to the poor plate shape is greatly reduced, the mechanical property is more uniform, the yield is improved, the labor productivity of the mill set is improved, and the extremely thin strip steel can be produced stably in a large quantity.
The headless or semi-headless rolling realizes stable rolling by keeping constant tension of the whole coil, and does not generate plate thickness change and plate convexity change caused by prediction error and adjustment error caused by roller thermal expansion and abrasion model, thereby obviously improving the plate thickness precision. The thickness precision of the ultrathin tropical zone can reach +/-30 mu m, and the qualification rate exceeds 99 percent. Ultra-thin hot bands also exhibit excellent elongation and normal microstructure.
As shown in fig. 2, the process for stably producing ultra-thin hot rolled strip steel by the endless rolling process comprises the following steps: continuous casting, rough rolling by a large-reduction rolling mill, induction heating, finish rolling and descaling, finish rolling, laminar cooling, high-speed flying shear splitting and coiling.
Continuous casting, namely casting a proper casting blank at a high drawing speed by adopting a straight arc-shaped continuous casting machine; rough rolling by a high reduction rolling mill, namely, reducing the casting blank into a proper intermediate blank by the rolling mill; induction heating, namely realizing the compensation heating of the intermediate billet, wherein the maximum temperature rise can reach 300 ℃, and the finish rolling force is reduced; finish rolling descaling, namely descaling and removing the iron scale on the surface of the strip steel by high-pressure water; finish rolling, namely, finish rolling by five racks to realize the thickness and the width required by a customer; laminar cooling, namely a laminar cooling device with a high-level water tank is adopted, a flow valve is adopted for controlling a collecting pipe, the flow of the collecting pipe is accurately controlled, the cooling speed of the strip steel is accurately controlled, and the mechanical property of the strip steel is effectively controlled. In a high-speed flying shear-headless production mode, strip steel with the thickness of 0.8-4mm is subjected to coil splitting and shearing.
The 0.8-1.5mm ultrathin hot-rolled strip steel produced by the endless rolling process is used as a substrate without phosphating treatment, and further research and development are carried out on the basis, so that the technical scheme of the invention is finally formed.
The following will explain the technical solution of the present invention in detail with reference to fig. 1.
Example 1
The invention provides a preparation method of a phosphatization-free plate based on a headless rolling process, which comprises the following steps:
(1) adopting 0.8mm ultrathin hot-rolled strip steel produced by a headless rolling process as a substrate without phosphating treatment; the surface unevenness of the substrate is less than or equal to 15I, and the roughness Ra: 2.0 μm, then the obtained substrate is sent into a continuous pickling machine for pickling after being subjected to an uncoiling process, a laser welding process and a phosphorus breaking and straightening process.
Laser welding in this step: the head-to-tail connection of front and back coils is realized by adopting a German and Mi octahh laser welding machine to realize the continuous production function; scale breaking, pulling and straightening: loosening the oxide scales on the surface of the hot-rolled strip steel and improving the strip steel shape through a withdrawal and straightening process; continuous acid washing: removing the surface iron scale by shallow groove turbulent flow type acid washing strip steel.
(2) Removing an oxide layer of the substrate by a continuous pickling line, and rinsing the substrate by deionized water to ensure the cleanliness of the surface of the substrate; wherein the technical indexes of the deionized water are as follows: electrical conductivity of<10 muS/cm, PH =6, chloride ion not more than 2.8mg/L, soluble SiO2≤0.2mg/L。
(3) Preparing a metal surface treating agent, wherein the metal surface treating agent is prepared from the following raw materials in parts by weight: 1 part of a silane coupling agent; 1 part of modified resin; 0.5 part of hydrolysis stabilizer; 1.5 parts of curing agent and 10 parts of alcohol; 60 parts of deionized water, and the preparation method comprises the following steps: adding 10 parts of alcohol, 5 parts of deionized water and 0.5 part of hydrolysis stabilizer into a preparation container in sequence, then adding 1 part of silane coupling agent and 1 part of modified resin into the preparation container under the condition of shearing and stirring, stirring and reacting for 1 hour at room temperature, after the stirring and reacting are finished, adding 1.5 parts of curing agent into the preparation container, uniformly stirring, and finally adding the rest deionized water into the preparation container to form the metal surface treating agent. The deionized water used in the process is the same substance as the deionized water used in step (2).
In this embodiment, the silane coupling agent is one or more of methacryloxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane; the modified resin is selected from one or more of modified acrylic resin, modified alkyd resin and modified polyester resin; the hydrolysis stabilizer is selected from one of nonionic acrylamide and fatty acid polyglycol ester; the curing agent is one of trioxymethylene and anhydrous ethylenediamine; the alcohol is selected from one or more of methanol, ethanol and propanol.
(4) And coating the metal surface treating agent on the surface of the substrate by a roller coating process after the rinsed substrate is subjected to a leveling process, drying, and coiling after drying to form a phosphatization-free steel coil for downstream users to use. Wherein the drying temperature is 200 ℃, the drying time is 2s, and the temperature of the plate surface of the phosphating-free plate discharged from the drying furnace is more than or equal to 50 ℃; and the roller coating process adopts a forward coating or reverse coating mode, a metal surface treating agent is uniformly coated on the upper surface and the lower surface of the rinsed substrate to form a coating film, and the coating film is dried to form the phosphating-free plate, wherein the weight of a single-surface coating film in the phosphating-free plate is more than or equal to 0.3g per square meter, and the film thickness of the coating film is 2 mu m.
In the step, the purpose of leveling is to control the surface roughness of the strip steel and remove the yield platform of the low-carbon mild steel; and (3) roller coating: the coating liquid is uniformly and effectively coated on the upper surface and the lower surface of the strip steel; drying: the coating liquid is solidified and effectively combined with the strip steel by heating by adopting waste heat, a burner and an electric heating mode.
Example 2
The invention provides a preparation method of a phosphatization-free plate based on a headless rolling process, which comprises the following steps:
(1) 1.0mm ultrathin hot-rolled strip steel produced by a headless rolling process is used as a substrate free of phosphating treatment; the surface unevenness of the substrate is less than or equal to 15I, and the roughness Ra: 0.7 μm, then the obtained substrate enters a continuous pickling machine for pickling after the processes of uncoiling, laser welding and phosphor breaking and straightening.
(2) Removing an oxide layer of the substrate by a continuous pickling line, and rinsing the substrate by deionized water to ensure the cleanliness of the surface of the substrate; wherein, the technical indexes of the deionized water are as follows: electrical conductivity<10 mu S/cm, PH =6, chloride ion less than or equal to 2.8mg/L, soluble SiO2≤0.2mg/L。
(3) Preparing a metal surface treating agent, wherein the metal surface treating agent is prepared from the following raw materials in parts by weight: 2 parts of a silane coupling agent; 3 parts of modified resin; 1.4 parts of hydrolysis stabilizer; 2.2 parts of curing agent and 17 parts of alcohol; 73 parts of deionized water, and the preparation method comprises the following steps: adding 17 parts of alcohol, 11 parts of deionized water and 1.4 parts of hydrolysis stabilizer into a preparation container in sequence, then adding 2 parts of silane coupling agent and 3 parts of modified resin into the preparation container under the condition of shearing and stirring, stirring and reacting for 2.2 hours at room temperature, after the stirring and reacting are finished, adding 2.2 parts of curing agent into the preparation container, uniformly stirring, and finally adding the rest deionized water into the preparation container to form the metal surface treating agent. The deionized water used in the process is the same substance as the deionized water used in step (2).
In this embodiment, the silane coupling agent is one or more of methacryloxy silane, vinyltrimethoxy silane, vinyltriethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, propyltrimethoxy silane, propyltriethoxy silane; the modified resin is selected from one or more of modified acrylic resin, modified alkyd resin and modified polyester resin; the hydrolysis stabilizer is selected from one of nonionic acrylamide and fatty acid polyglycol ester; the curing agent is one of trioxymethylene and anhydrous ethylenediamine; the alcohol is selected from one or more of methanol, ethanol and propanol.
(4) And coating the metal surface treating agent on the surface of the substrate by a roller coating process after the rinsed substrate is subjected to a leveling process, drying, and coiling after drying to form a phosphatization-free steel coil for downstream users to use. Wherein the drying temperature is 280 ℃, the drying time is 5s, and the temperature of the plate surface of the phosphating-free plate out of the drying furnace is more than or equal to 50 ℃; and the roller coating process adopts a forward coating or reverse coating mode, the metal surface treatment agent is uniformly coated on the upper surface and the lower surface of the rinsed substrate to form a coating film, and a phosphating-free plate is formed after drying, wherein the weight of a single-sided coating film in the phosphating-free plate is more than or equal to 0.3 g/square meter, and the film thickness of the coating film is 2 micrometers.
Example 3
The invention provides a preparation method of a phosphatization-free plate based on a headless rolling process, which comprises the following steps:
(1) 1.2mm ultrathin hot-rolled strip steel produced by a headless rolling process is used as a substrate without phosphating treatment; the surface unevenness of the substrate is less than or equal to 15I, and the roughness Ra: 1.8 mu m, and then the obtained substrate enters a continuous pickling machine for pickling after the processes of uncoiling, laser welding and phosphor breaking and straightening.
(2) Removing an oxide layer of the substrate by a continuous pickling line, and rinsing the substrate by deionized water to ensure the cleanliness of the surface of the substrate; wherein the technical indexes of the deionized water are as follows: electrical conductivity of<10 mu S/cm, PH =7, chloride ion less than or equal to 2.8mg/L, soluble SiO2≤0.2mg/L。
(3) Preparing a metal surface treating agent, wherein the metal surface treating agent is prepared from the following raw materials in parts by weight: 4 parts of a silane coupling agent; 2 parts of modified resin; 2.3 parts of a hydrolysis stabilizer; 1.8 parts of curing agent and 19 parts of alcohol; 80 parts of deionized water, and the preparation method comprises the following steps: adding 19 parts of alcohol, 15 parts of deionized water and 2.3 parts of hydrolysis stabilizer into a preparation container in sequence, then adding 4 parts of silane coupling agent and 2 parts of modified resin into the preparation container under the condition of shearing and stirring, stirring and reacting for 3.4 hours at room temperature, after the stirring and reacting are finished, adding 1.8 parts of curing agent into the preparation container, uniformly stirring, and finally adding the rest deionized water into the preparation container to form the metal surface treating agent. The deionized water used in the process is the same substance as the deionized water used in step (2).
In this embodiment, the silane coupling agent is one or more of methacryloxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane; the modified resin is selected from one or more of modified acrylic resin, modified alkyd resin and modified polyester resin; the hydrolysis stabilizer is selected from one of nonionic acrylamide and fatty acid polyglycol ester; the curing agent is one of trioxymethylene and anhydrous ethylenediamine; the alcohol is selected from one or more of methanol, ethanol and propanol.
(4) And coating the metal surface treating agent on the surface of the substrate by a roller coating process after the rinsed substrate is subjected to leveling process, drying, and coiling after drying to form a phosphating-free steel coil for downstream users to use. Wherein the drying temperature is 330 ℃, the drying time is 8s, and the temperature of the plate surface of the phosphating-free plate out of the drying furnace is more than or equal to 50 ℃; and the roller coating process adopts a forward coating or reverse coating mode, a metal surface treating agent is uniformly coated on the upper surface and the lower surface of the rinsed substrate to form a coating film, and the coating film is dried to form the phosphating-free plate, wherein the weight of a single-surface coating film in the phosphating-free plate is more than or equal to 0.3g per square meter, and the film thickness of the coating film is 2 mu m.
Example 4
The invention provides a preparation method of a phosphatization-free plate based on a headless rolling process, which comprises the following steps:
(1) 1.5mm ultrathin hot-rolled strip steel produced by a headless rolling process is used as a substrate free of phosphating treatment; the surface unevenness of the substrate is less than or equal to 15I, and the roughness Ra: 0.5 μm, then the obtained substrate is sent into a continuous pickling machine for pickling after being subjected to uncoiling, laser welding and phosphorus breaking and straightening.
(2) Removing an oxide layer of the substrate by a continuous pickling line, and rinsing the substrate by deionized water to ensure the cleanliness of the surface of the substrate; wherein the technical indexes of the deionized water are as follows: electrical conductivity<10 mu S/cm, PH =7, chloride ion less than or equal to 2.8mg/L, soluble SiO2≤0.2mg/L。
(3) Preparing a metal surface treating agent, wherein the metal surface treating agent is prepared from the following raw materials in parts by weight: 5 parts of a silane coupling agent; 5 parts of modified resin; 2.5 parts of hydrolysis stabilizer; 2.5 parts of curing agent and 25 parts of alcohol; 86 parts of deionized water, and the preparation method comprises the following steps: adding 25 parts of alcohol, 20 parts of deionized water and 2.5 parts of hydrolysis stabilizer into a preparation container in sequence, then adding 5 parts of silane coupling agent and 5 parts of modified resin into the preparation container under the condition of shearing and stirring, stirring and reacting for 3.5 hours at room temperature, after the stirring and reacting are finished, adding 2.5 parts of curing agent into the preparation container, uniformly stirring, and finally adding the rest deionized water into the preparation container to form the metal surface treating agent. The deionized water used in the process is the same substance as the deionized water used in step (2).
In this embodiment, the silane coupling agent is one or more of methacryloxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane; the modified resin is selected from one or more of modified acrylic resin, modified alkyd resin and modified polyester resin; the hydrolysis stabilizer is selected from one of nonionic acrylamide and fatty acid polyglycol ester; the curing agent is one of trioxymethylene and anhydrous ethylenediamine; the alcohol is selected from one or more of methanol, ethanol and propanol.
(4) And coating the metal surface treating agent on the surface of the substrate by a roller coating process after the rinsed substrate is subjected to a leveling process, drying, and coiling after drying to form a phosphatization-free steel coil for downstream users to use. Wherein the drying temperature is 350 ℃, the drying time is 10s, and the temperature of the plate surface of the phosphating-free plate out of the drying furnace is more than or equal to 50 ℃; and the roller coating process adopts a forward coating or reverse coating mode, a metal surface treating agent is uniformly coated on the upper surface and the lower surface of the rinsed substrate to form a coating film, and the coating film is dried to form the phosphating-free plate, wherein the weight of a single-surface coating film in the phosphating-free plate is more than or equal to 0.3g per square meter, and the film thickness of the coating film is 2 mu m.
Four different sized phosphatized panels were formed therefrom according to the invention as described in examples 1-4 above.
The method comprises the following steps of carrying out a plastic spraying experiment by taking four phosphating-free plates with different specifications as an experimental group and a control group (steel plates formed by a traditional phosphating process), and detecting the aspects of binding force, adhesiveness, environmental protection and corrosion resistance, wherein the detection data are as follows:
serial number Examples Coating bonding force Adhesion of coating Environmental protection property Corrosion resistance Weldability
1 Example 1 Youyou (an instant noodle) T bend performance =2T No pollution Youyou (an instant noodle) Youyou (an instant noodle)
2 Example 2 Superior food T bending performance =2T No pollution Superior food Superior food
3 Example 3 Superior food T bending performance =2T No pollution Superior food Superior food
4 Example 4 Superior food T-bendPerformance =2T No pollution Superior food Superior food
5 Phosphating Youyou (an instant noodle) T bending performance =3T Heavy pollution Youyou (an instant noodle) Superior food
In summary, it can be seen that: the phosphating-free plate is a pollution-free process, and the phosphating plate is a heavy pollution process. The T bending performance of the phosphating-free plate is 2T, the T bending performance of the phosphating-free plate is 3T, and the adhesiveness of a phosphating-free coating is superior to that of the phosphating-free plate. Other coatings are comparable in both adhesion, corrosion resistance and weldability. The performance of the phosphating-free plate is far better than that of a phosphating plate.
The application cases of the phosphorus-free plate prepared by the invention are as follows:
example 5: high-low switch cabinet panel application. Spraying orange peel plastic, wherein the plastic layer is 60-80 mu m, the baking temperature is 180-220 ℃, and the baking time is 30 minutes. The marking detection shows that the requirement of grade 0 is met, and the reverse knocking detection shows that no plastic powder flakes fall off, so that the use requirement of customers is met.
Example 6: the box transformer substation cabinet door panel meets the requirements of customers by bending, punching and welding in the aspect of the forming process. The thickness of the plastic spraying layer is 80-100 mu m, the baking temperature is 200 ℃, and the baking time is 20 min. And the impact tests are qualified.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (10)

1. The preparation method of the phosphating-free plate based on the endless rolling process is characterized by comprising the following steps of:
(1) adopting 0.8-1.5mm ultrathin hot-rolled strip steel produced by a headless rolling process as a substrate without phosphating treatment;
(2) removing an oxide layer of the substrate by a continuous pickling line, and rinsing the substrate by deionized water to ensure the cleanliness of the surface of the substrate; wherein the technical indexes of the deionized water are as follows: electrical conductivity of<10 mu S/cm, pH value of 6-7, chloride ion less than or equal to 2.8mg/L and soluble SiO2≤0.2mg/L；
(3) Preparing a metal surface treating agent, wherein the metal surface treating agent is prepared from the following raw materials in parts by weight: 1-5 parts of a silane coupling agent; 1-5 parts of modified resin; 0.5-2.5 parts of hydrolysis stabilizer; 1.5-2.5 parts of curing agent and 10-25 parts of alcohol; 60-86 parts of deionized water, and is prepared by the following preparation method, wherein the preparation process comprises the following steps: sequentially adding 10-25 parts of alcohol, 5-20 parts of deionized water and 0.5-2.5 parts of hydrolysis stabilizer into a preparation container, then adding 1-5 parts of silane coupling agent and 1-5 parts of modified resin into the preparation container under the condition of shearing and stirring, stirring and reacting for 1-3.5 hours at room temperature, adding 1.5-2.5 parts of curing agent into the preparation container after the stirring and reacting are finished, uniformly stirring, and finally adding the rest deionized water into the preparation container to form the metal surface treating agent; wherein the deionized water used in the step (3) is the same as the deionized water used in the step (2);
(4) and (3) coating the metal surface treating agent prepared in the step (3) on the surface of the substrate rinsed in the step (2) through a roller coating process, and drying to prepare the phosphating-free plate, wherein the drying temperature is 200-350 ℃, the drying time is 2-10s, and the plate surface temperature of the phosphating-free plate out of a drying furnace is more than or equal to 50 ℃.
2. The preparation method of the non-phosphatized plate based on the endless rolling process as claimed in claim 1, wherein the surface unevenness of the substrate is not more than 15I, and the roughness Ra: 0.5 to 2.0 μm.
3. The method for preparing the phosphatized free board based on the endless rolling process as claimed in claim 2, wherein the silane coupling agent is one or more of methacryloxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, propyl trimethoxy silane and propyl triethoxy silane.
4. The method for preparing the phosphatized free board based on the endless rolling process according to claim 2, wherein the modified resin is selected from one or more of modified acrylic resin, modified alkyd resin and modified polyester resin.
5. The method for preparing the phosphated-free plate based on the endless rolling process of claim 2, wherein the hydrolysis stabilizer is selected from one of nonionic acrylamide and fatty acid polyglycol ester.
6. The preparation method of the phosphatized free board based on the endless rolling process as claimed in claim 2, wherein the curing agent is one of trioxymethylene and anhydrous ethylenediamine; the alcohol is selected from one or more of methanol, ethanol and propanol.
7. The preparation method of the phosphating-free plate based on the endless rolling process according to claim 2, wherein the roller coating process adopts a forward coating or reverse coating mode, the metal surface treatment agent is uniformly coated on the upper surface and the lower surface of the rinsed substrate to form a coating film, the coating film is dried to form the phosphating-free plate, the weight of a single-surface coating film in the phosphating-free plate is more than or equal to 0.3g per square meter, and the film thickness of the coating film is 2 μm.
8. The method for preparing the phosphating-free plate based on the endless rolling process is characterized in that the base plate enters a continuous pickling machine for pickling after uncoiling, laser welding and phosphorus breaking and straightening.
9. The method for preparing the phosphatized free board based on the endless rolling process of claim 8, wherein the rinsed substrate is further processed by a flattening procedure, and then a metal surface treatment agent is coated on the surface of the substrate by a roller coating process and then dried, and after drying, the substrate is coiled to form a phosphatized free steel coil for downstream users to use.
10. A phosphatized free slab produced based on a endless rolling process, produced based on the method of any one of claims 1 to 9.
CN202210709428.8A 2022-06-22 2022-06-22 Phosphating-free plate based on endless rolling process and preparation method thereof Pending CN114773937A (en)

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Application publication date: 20220722