CN114351072B - Production process of alloyed plated steel bar - Google Patents

Production process of alloyed plated steel bar Download PDF

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Publication number
CN114351072B
CN114351072B CN202111632164.2A CN202111632164A CN114351072B CN 114351072 B CN114351072 B CN 114351072B CN 202111632164 A CN202111632164 A CN 202111632164A CN 114351072 B CN114351072 B CN 114351072B
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steel bar
zinc
layer
alloy
induction heating
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CN114351072A (en
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李冲冲
曹博皓
杨腾
张雪莲
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North China Institute of Aerospace Engineering
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North China Institute of Aerospace Engineering
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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
    • C23C2/26After-treatment
    • C23C2/265After-treatment by applying solid particles to the molten coating
    • 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
    • C23C2/14Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18Removing excess of molten coatings from elongated material
    • C23C2/185Tubes; Wires
    • 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
    • C23C2/28Thermal after-treatment, e.g. treatment in oil bath
    • 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
    • C23C2/34Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36Elongated material
    • C23C2/38Wires; Tubes

Abstract

The invention relates to a production process of an alloyed plated steel bar, which is characterized in that the steel bar is subjected to environment-friendly hot dip plating treatment, before the plating solution on the surface of a steel piece is solidified, the molten liquid plating solution after dip plating is taken as a solvent, alloy elements are sprayed into the solvent, and then the alloy layer is only subjected to induction heating by the skin effect of high-frequency induction heating, so that the surface layer of the plated layer is further alloyed to obtain the alloyed plated steel bar of the gradient alloyed plated layer containing the alloy elements, wherein the gradient alloyed plated layer is formed by taking a substrate as a bottom layer and transiting from the surface layer to the surface layer. The process can provide protective measures to comprehensively control corrosion of the steel bars more effectively and moderately at a moderate cost, prolong the service life of the reinforced concrete structure to the maximum extent, and reduce the maintenance cost.

Description

Production process of alloyed plated steel bar
Technical Field
The invention belongs to the technical field of metal corrosion protection, and particularly relates to a production process of an alloyed plated steel bar.
Background
Under the great strategy of ocean and new construction, the reinforced concrete as the core construction material of the Chinese 'building crazy magic' plays a role of importance. The marine infrastructure construction (such as harbor wharfs, tunnels, cross-sea bridges, marine drilling platforms and the like) is very large in scale, various marine reinforced concrete construction projects and marine equipment investment are huge, and the service life and durability of the marine reinforced concrete construction projects directly influence national economy sustainable development strategy. The steel bar is an important framework material of the concrete structure, and the corrosion resistance of the steel bar is directly related to the durability of the reinforced concrete structure. The problems of concrete cracking and structural damage caused by steel bar corrosion are increasingly serious due to the characteristics of the steel bar and the change of the surrounding environment, and large-scale maintenance is required for many marine infrastructures which do not reach the service life, so that direct and indirect losses caused by steel bar corrosion are far beyond the imagination of people. Therefore, how to take effective measures and countermeasures to prevent the premature failure of the marine concrete structure caused by the corrosion of the steel bars and ensure the expected service life of the building becomes a hot spot problem of great concern in academic circles and engineering circles at home and abroad.
The surface coating protection is one of the important ways to solve the problem of corrosion prevention of the steel bar and improve the corrosion resistance of the steel bar and the durability of the concrete structure. Therefore, the development of the novel high corrosion-resistant coating steel bar and the preparation technology has great safety and economic significance for improving the durability and the service life of the reinforced concrete structure, reducing the cost and the investment of the later maintenance of the concrete structure and promoting the construction of the ocean and the country.
Aiming at the corrosion problem of the steel bar in reinforced concrete, china patent 201320220754.9 discloses a zinc and epoxy double-coating steel bar and a processing method, wherein a zinc layer is obtained by adopting thermal spraying on the steel bar, the thickness of the zinc layer is 50-100 mu m, the zinc layer is not metallurgically bonded with a matrix, the zinc layer is poor in bending resistance, and the zinc layer and the matrix easily cause the problem of cracking of the zinc layer in the steel bar bending process, so that the integrity of the coating is affected. Patent CN 110923616a discloses a rare earth aluminum alloy coated steel bar by thermal spraying, which is characterized in that rare earth aluminum alloy wires are sprayed on a steel bar substrate subjected to surface cleaning treatment in a thermal spraying manner to form a thermal spraying rare earth aluminum alloy coated layer, the thermal spraying coating and the substrate are combined in a mechanical embedding manner, and the coated steel bar has the defects of poor thermal spraying bonding force, high production cost and the like.
Disclosure of Invention
Aiming at the urgent need of the current ocean engineering on the high corrosion resistant steel bar and a series of problems existing in the existing steel bar protection technology, the invention provides a hot dip galvanized aluminum alloy plating layer/coating multi-system protection layer alloying plating layer steel bar and a production process thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a production process of an alloying coating steel bar is characterized in that: the method comprises the steps of carrying out environment-friendly hot dip plating treatment on the steel bar, taking molten liquid plating solution after dip plating as a solvent before the plating solution on the surface of the steel bar is solidified, spraying alloy elements into the solvent, and carrying out induction heating on the alloy layer only by the skin effect of high-frequency induction heating, so that the surface layer of the coating is further alloyed to obtain the alloy-coated steel bar with the gradient alloy coating which takes a matrix as a bottom layer and is in transition with the surface layer.
The specific steps of the production process of the alloyed plated steel bar are as follows:
1. environment-friendly hot galvanizing
The following three schemes can be adopted:
the first scheme is as follows: passing the environment-friendly rust-removed steel bar through a closed tubular resistance furnace (the temperature is 450-700 ℃) filled with inert gas (mainly nitrogen or argon) or inert gas/hydrogen mixed gas, and then horizontally and rapidly passing through molten zinc liquid (450-480 ℃) to plate a layer of zinc on the surface of the steel bar;
the second scheme is as follows: passing the environment-friendly rust-removed steel bar through a closed ceramic tube or quartz tube filled with inert gas (mainly nitrogen or argon) or inert gas/hydrogen mixed gas, simultaneously applying high-frequency induction heating, and then horizontally and rapidly passing through molten zinc liquid to plate a layer of zinc on the surface of the steel bar;
third scheme: plating auxiliary and drying the steel bar subjected to environment-friendly rust removal, then entering molten zinc liquid to plate a layer of zinc on the surface of the steel bar, and degreasing and rust removal can be carried out by adopting traditional pretreatment, and hot galvanizing can be carried out after plating auxiliary;
further, the environmental protection rust removal of the three hot galvanizing schemes mainly comprises at least one of mechanical rust removal (including but not limited to shot blasting rust removal, steel brush rust removal and the like), laser rust removal and environmental protection rust remover rust removal; the method has the advantages that the whole process does not involve any chemical agent discharge, in particular the first two schemes do not need plating assistance, water washing and other procedures, and the method has the advantages of short process flow, energy conservation, emission reduction, environmental protection, high efficiency and the like.
2. Galvanized layer induction remelting and alloying
The method can be realized by the following steps:
the first scheme is as follows: after the steel bar is galvanized, powder spraying alloying is carried out before the zinc liquid on the surface of the steel bar is solidified, high-frequency induction heating is carried out under the protection of inert gas, the high-temperature air knife is used for blowing and water cooling, the zinc feeding amount is controlled, molten zinc liquid on the surface of the steel bar is used as a solvent, sprayed metal or alloy powder is used as solute, the coating is kept in a molten state through inert gas protection induction heating, the sprayed alloy powder and molten zinc are subjected to metallurgical reaction by utilizing the skin effect of the high-frequency induction heating, the coating is alloyed, then an alloying coating layer with a certain thickness is formed on the surface of the steel bar through air knife blowing and rapid water cooling, and then a gradient alloying coating layer which is formed by taking zinc or zinc-iron alloy as a bottom layer and transiting to a surface layer is obtained, and metallurgical bonding is carried out among the coating layers;
the second scheme is as follows: before the galvanized steel bar is solidified, the surface of the galvanized steel bar is covered with an alloy layer by hot spraying metal or alloy (powder or wire) under the protection of inert gas, then gas-shielded high-frequency induction heating is carried out, so that the hot spraying alloy layer is quickly heated to a temperature above the melting point of the alloy, and is subjected to metallurgical reaction with the preplating zinc layer to form alloying with metallurgical bonding, and then the alloying cover layer with metallurgical bonding is formed by blowing through an air knife and quickly water-cooling, thus obtaining the alloying plating steel bar of the gradient alloying plating layer which uses zinc or zinc-iron alloy as the bottom layer to transition to the surface layer.
Further, after the steel bar is galvanized, or the alloyed plated steel bar obtained by the two schemes is quickly heated to 550-560 ℃ within a few seconds by adopting a medium-high frequency induction heating device, so that the galvanized alloy layer and the galvanized iron matrix are subjected to diffusion reaction, and the alloyed plated steel bar with metallurgical bonding is formed from the inside of the matrix to the surface layer.
The high-frequency induction heating frequency is 50-100KHz, and the heating depth is 1-3mm; the frequency of the medium-high frequency induction heating is 1-50 kHz, the heating thickness is not less than 10mm, and the preparation of the zinc-iron alloy layer after adding alloy elements can be realized by adjusting the frequency range of the high-frequency and medium-high frequency induction heating.
Further, the whole production process is horizontal production, and the horizontal galvanization mode can be overflow or non-overflow;
further, the equipment system involved in the production process mainly comprises an ammonia decomposition device (for providing nitrogen and hydrogen required by production), a control valve, a high-frequency induction heating system (comprising protection heating and induction remelting treatment), a closed zinc melting device, a spraying equipment system (thermal spraying or common spraying), a quartz tube or ceramic tube (closed environment), a plating control system (a system for controlling the work of an air knife), and a steel bar cutting or winding system.
The closed zinc melting device comprises a working pool and a supply pool, wherein the working pool is communicated with the lower part of the supply pool, the upper part of the working pool is closed, the upper part of the supply pool is communicated with the atmosphere, through holes for long materials to enter and exit are formed in the upper parts of the working pool and the supply pool at the same height, and all the through holes are connected together through quartz pipes in sequence to form a channel for steel bars to pass through; the working tank and the replenishing tank are both filled with treatment liquid, and the liquid level of the working tank is higher than the position of the upper end of the through hole.
The working tank and the replenishing tank are provided with heating systems, and the heating modes of the heating systems can be internal heating, gas heating, induction heating and the like.
The working pool and the bottom of the replenishing pool are in a communicating design, long material passing holes are formed in two sides of the upper part of the middle working pool, and an anti-overflow device is arranged at the passing holes.
The top of the working pool is of a sealing design and is provided with an air suction hole, the air suction hole is connected with a pressure control compensation system, the liquid level of the working pool is ensured to be higher than the upper end of the through hole during working, automatic pressure compensation of the working pool is realized, and the pressure in the working pool is kept constant.
The bottom of the replenishing pool is communicated with the middle working pool, namely, a communication hole is formed in the intersecting position of the replenishing pool and the working pool, and the liquid level of the replenishing pool is higher than the upper side of the communication hole during working.
The upper part of the replenishment pool is of a non-airtight design, long material passing holes are formed in two sides of the replenishment pool as well, and the working pool is connected with the passing holes of the replenishment pool through airtight quartz pipe fittings with the same shape and size as the passing holes; the shape of the through hole can be round hole shape, rectangle, etc. to adapt to the passing requirement of the reinforcing steel bars with different specifications.
Further, the induction remelting process is also in a closed environment protected by inert gas (usually nitrogen or argon and the like), so that rapid oxidation of a coating in the induction remelting or alloying process is avoided.
Further, the alloy coated steel bar is an alloy coated steel bar with zinc or zinc alloy (zinc aluminum series coating such as zinc aluminum (Galfan), zinc Aluminum Magnesium (ZAM), zinc aluminum silicon (Galvalum) and the like) or aluminum as a bottom layer.
Further, the alloy material in the alloying process may be at least one of pure metal (such as aluminum, magnesium, nickel, cobalt, zirconium, titanium, etc.), binary or multi-element alloy, powder of metal oxide, and the powder is preferably nano-sized powder.
The nitrogen temperature purged by the high-temperature air knife is 150-200 ℃, and the high-temperature air knife is used for removing zinc liquid attached to the surface of the steel bar by wiping so as to control the thickness of an attached molten zinc layer to be 30-50 mu m, and ensure uniformity, such as the thickness of the molten zinc layer to be 30 mu m, 35 mu m, 40 mu m, 45 mu m, 48 mu m and the like; the nitrogen temperature in the process of purging by an air knife and rapid water cooling is 35-100 ℃, and the thickness of a plating layer is controlled to be 50-80 mu m, such as the thickness of an alloying plating layer is 52, 54, 56, …, 76, 78, 80 mu m, and the like.
Furthermore, the alloy plating layer can also carry out alloying plating treatment on steel wires, structural members (such as section steel, channel steel and the like), steel plates, angle steel, round steel and other metal products, and the process or method improvement and the like which do not deviate from the essential connotation of the invention belong to the protection scope of the invention.
Further, the application fields of the alloyed plated steel bar include, but are not limited to, highways, bridges, tunnels, buildings, harbor facilities, etc.
The coating obtained by the invention is essentially different from the traditional alloy coating, so that the invention has the following beneficial effects:
1) The components of the alloy plating layer can be controlled by controlling the loading rate or the utilization rate of sprayed alloy powder, the purposes of accurately adjusting and controlling the plating layer are realized, the problem that the components of the alloy plating solution are difficult to control due to dilution effect in the second zinc pot filled with the alloy solution after the zinc layer plated in the process of plating the alloy layer is melted in the prior art is avoided, and the problems that the components of the alloy plating solution are changed and the components of the alloy plating solution are difficult to control in the traditional double plating process are effectively solved.
2) Alloying the coating component by utilizing inert gas protection induction remelting, and forming gradient metallurgical bonding with the galvanized layer matrix;
3) The hot dip coating and spray remelting alloying process solves the problem of poor binding force between a coating and a substrate in a single hot spray process; the invention firstly dips zinc, then alloys the plating layer by spraying alloy element, then induction remelting is carried out by induction heating, the purpose of zinc plating is to provide sacrificial anode protection, the alloy element is added to further improve corrosion resistance and other comprehensive performances of the plating layer, and the influence on the overall performance of the substrate can be reduced by a high-frequency induction heating mode, the added type and the added amount of the alloy can be effectively controlled by a spraying mode, and the large influence on the performance of the substrate caused by remelting the plated alloy by a direct muffle furnace heat treatment mode is avoided.
4) The pretreatment process of mechanical rust removal and protective gas induction heating reduction has the advantages of remarkable environmental protection and emission reduction, and thoroughly solves the pollution problem in the pretreatment before galvanization; the whole hot dipping process does not use any chemical agent and does not generate any waste or pollutant.
5) Solves the technical problems of easy miss plating and difficult hot plating in the traditional solvent method hot-dip plating process of high aluminum alloy.
6) The oil stains and the like on the surface of the steel bar can be ablated by the instantaneous high temperature in the induction heating or laser cleaning (laser rust removal) process, so that the effect of purifying the surface is achieved.
The remarkable progress of the invention is:
the binding force is good: compared with the alloy coated steel bar obtained by a single thermal spraying process, the process can realize metallurgical bonding between the alloy coating and the matrix, and obviously improve the bonding force between the coating and the matrix and the compactness of the coating.
The adaptability is strong: compared with the traditional hot-dip alloy process, the preparation method of the alloy coating provided by the invention has the advantages that the alloy coating is various in types, the components are easy to control, the alloy coatings with different performances can be obtained by adjusting the types and the contents of sprayed metal or alloy, the production adaptability is strong, the production line is not required to be changed greatly, and the flexible adjustment is realized, so that the requirements of customers on steel bar products with different components and different performances are met.
Cost/energy saving: the traditional hot galvanizing pot has the advantages that the zinc melting amount is up to tens tons, the cost investment is greatly increased, and the heating is needed to ensure the heat supply of zinc liquid, so that the preparation process has low requirements on the zinc melting amount, a small zinc melting device can be adopted, the operation of a production line can be met by a few tons of zinc melting, in addition, the induction heating process can provide heat for the steel bars, and the heat supply requirement of the zinc melting device is reduced.
Environmental protection and high efficiency: the method completely realizes environment-friendly hot-dip coating, thoroughly eliminates pollution problems caused by traditional acid washing, alkali washing, water rinsing and the like, realizes clean production of galvanized products, has great guiding effect on carbon neutralization and carbon reaching peaks in the zinc plating industry, and is suitable for preparation and production of almost all alloy plating layers.
The process can provide protective measures to comprehensively control corrosion of the steel bars more effectively and moderately at a moderate cost, prolong the service life of the reinforced concrete structure to the maximum extent, and reduce the maintenance cost.
The closed zinc melting device adopts ingenious conception and utilizes the pressure difference principle to design the processing device for hot-dip coating of the steel bars, and the working pool of the zinc melting device is of a closed structure, so that the long material hot-dip coating production process is more energy-saving and environment-friendly.
Drawings
FIG. 1 is a flow chart of the production process in the invention.
The wire rod is shown in the figure 1; 2. environmental protection rust removal; 3. sealing induction heating; 4. horizontal galvanization; 5. zinc layer control; 6. powder spraying; 7. induction remelting; 8. alloy layer control; 9. cooling; 10. and (5) passivating.
Fig. 2 is a schematic view of the structure of the alloyed plated steel bar in the invention.
1, a steel matrix; 2. a zinc plating layer; 3. and (3) an alloying layer.
Detailed Description
The present invention will be further described with reference to examples and drawings, which should not be construed as limiting the scope of the present application.
As shown in fig. 1, the production process flow chart of the alloyed plated steel bar in the invention is shown; the wire rod is shown in the figure 1; 2. environmental protection rust removal; 3. sealing induction heating; 4. horizontal galvanization; 5. zinc layer control; 6. powder spraying; 7. induction remelting; 8. alloy layer control; 9. cooling; 10. and (5) passivating.
Fig. 2 is a schematic diagram showing the coating structure of the alloyed coated steel bar obtained by the invention; 1, a steel matrix; 2. a zinc plating layer; 3. and the alloying layers are metallurgically bonded.
The production process of the alloyed plated steel bar comprises the following steps: the alloyed plated steel bar is firstly subjected to environment-friendly hot galvanizing, and then is obtained through induction remelting and alloying of a galvanized layer.
The method specifically comprises the following steps:
1. environment-friendly hot galvanizing process
The following three schemes can be adopted:
(1) Passing the steel bar subjected to environment-friendly rust removal through a closed tubular resistance furnace (the temperature is 450-700 ℃) filled with inert gas (mainly nitrogen or argon) or inert gas/hydrogen mixed gas, and then horizontally and rapidly passing through molten zinc liquid (450-480 ℃) to plate a layer of molten zinc on the surface of the steel bar;
(2) The steel bar subjected to environmental protection rust removal passes through a closed ceramic tube or a quartz tube filled with inert gas (mainly nitrogen or argon) or inert gas/hydrogen mixed gas, high-frequency induction heating is applied at the same time, the frequency is 10-200 kHz, the surface temperature of the steel bar reaches 500-800 ℃, then the steel bar horizontally and rapidly passes through molten zinc liquid, and the surface of the steel bar is plated with a layer of molten zinc by utilizing metallurgical reaction between high Wen Xiatie-zinc.
(3) Plating the steel bar subjected to environment-friendly rust removal with a molten zinc solution (450-480 ℃) to plate a layer of molten zinc on the surface of the steel bar, and degreasing and rust removal and plating assistance can be carried out by adopting traditional pretreatment;
further, the environmental protection rust removal of the three hot galvanizing schemes mainly comprises at least one of mechanical rust removal (including but not limited to shot blasting rust removal, steel brush rust removal and the like), laser rust removal and environmental protection rust remover rust removal; the method has the advantages that the whole process does not involve any chemical agent discharge, in particular the first two schemes do not need plating assistance, water washing and other procedures, and the method has the advantages of short process flow, energy conservation, emission reduction, environmental protection, high efficiency and the like.
2. Galvanized layer induction remelting and alloying
Melting alloy powder by utilizing induction remelting, heating the alloy powder to be above the melting point of the alloy by using high-frequency induction heating, and carrying out alloying reaction with molten zinc to obtain an alloying coating, wherein the alloying coating can be realized by adopting the following modes:
the first scheme is as follows: after the steel bar is galvanized, powder spraying alloying is carried out before the zinc liquid on the surface of the steel bar is solidified, high-frequency induction heating is carried out under the protection of inert gas, then blowing and water cooling are carried out through an air knife, the zinc loading amount is controlled, molten zinc liquid on the surface of the steel bar is taken as a solvent, sprayed metal or alloy powder and the like are taken as solutes, the plating layer is kept in a molten state through inert gas protection induction heating, the sprayed alloy powder and molten zinc are subjected to metallurgical reaction by utilizing the skin effect of the high-frequency induction heating, the plating layer is alloyed, an alloying covering layer with a certain thickness is formed on the surface of the steel bar, and then the gradient alloy plating layer (zinc-iron alloy-zinc alloy) which is formed by taking zinc-iron alloy as a bottom layer and transiting to a surface layer is obtained.
The frequency of the high-frequency induction heating is 50-200KHz, the heating depth is 1-3mm, the preferred heating frequency is 50-100KHz and 100-150KHz, and the thickness of the zinc coating can be controlled by high-temperature blowing, so that the surface of the zinc coating is uniform.
The second scheme is as follows: after the galvanized steel bar is solidified, metal or alloy (powder or wire material is adopted, when the wire material is adopted, the wire material is melted and sprayed on the surface of the galvanized steel bar) is coated with an alloy layer by hot spraying under the protection of inert gas, then gas-shielded high-frequency induction heating is carried out, so that the hot spraying alloy layer is rapidly heated to a temperature above the melting point of the alloy, and metallurgical reaction is carried out on the hot spraying alloy layer and the preplated zinc layer to form an alloying coating layer with metallurgical bonding, and then the alloying coating steel bar taking zinc as a bottom layer is obtained by blowing through an air knife and rapidly water-cooling.
Further, after the steel bar is galvanized, or the alloyed plated steel bar obtained by the two schemes is quickly heated to (550-560 ℃) within a few seconds by adopting a medium-high frequency induction heating device, so that the galvanized alloy layer and the galvanized iron matrix are subjected to diffusion reaction, and the alloyed plated steel bar with metallurgical bonding and containing the pre-sprayed alloy elements is formed. The frequency of medium-high frequency induction heating is 1-50 kHz, the heating depth is not less than 10mm, the heating depth is relatively wide at the moment, the medium-high frequency induction heating can act on the inside of a matrix, the matrix and a zinc layer are enabled to be diffused, a product with relatively high alloy elements can be obtained to the greatest extent, the weldability and the coating property are improved, cracking and falling are avoided, the comprehensive performance of the product is enriched and improved, and the method has outstanding advantages for severe working environments such as ocean steel bars and the like.
In the first-step environment-friendly hot galvanizing method, the steel bars are heated to about 700 ℃ in an induction way, so that the temperature of the surfaces of the steel bars meets the requirement, the heat loss of a zinc pot is reduced, and certain reaction of zinc and iron is promoted; the second step of induction remelting and alloying aims to maintain the molten state of zinc and enable the alloy powder to be melted rapidly, molten zinc liquid on the surface of the steel bar is used as a solvent, sprayed metal or alloy powder and the like are used as solutes, so that the alloy powder can react with the zinc liquid, and after solidification, the metal powder can be covered on the surface to form an alloying covering layer. Finally, after the alloyed plating layer is obtained, induction heating is used again to enable the zinc and the iron of the matrix to have diffusion reaction, so that the weldability and the coating property of the steel bar are further enhanced.
Further, the whole production process is horizontal production, and the horizontal galvanization mode can be overflow type or non-overflow type;
further, the equipment system involved in the production process and method mainly comprises an ammonia decomposition device (for providing nitrogen and hydrogen required for production) and a control valve, a high-frequency induction heating system (comprising protection heating and induction remelting treatment), a closed zinc melting device, a spraying equipment system (comprising thermal spraying or common spraying), a quartz tube or ceramic tube (closed environment), a plating control system and a steel bar cutting or winding system.
Further, the induction remelting process is also in a closed environment protected by inert gas (usually nitrogen or argon and the like), so that rapid oxidation of a coating in the induction remelting or alloying process is avoided, and meanwhile, the change of alloy components of the coating is avoided.
Further, the alloy coated steel bar is an alloy coated steel bar with zinc or zinc alloy (zinc aluminum series coating such as zinc aluminum (Galfan), zinc Aluminum Magnesium (ZAM), zinc aluminum silicon (Galvalum) and the like) or aluminum as a bottom layer.
Further, the alloy material in the alloying process can be at least one of pure metal (such as aluminum, magnesium, nickel, cobalt, zirconium, titanium, etc.), binary or multi-element alloy, and metal oxide powder, and the powder is preferably nano-scale powder, and can be rapidly melted by induction heating. The temperature of induction heating is regulated by controlling the frequency and the heating time, and inert protective gas is applied during induction heating to prevent the plating layer alloying from oxidation and the plating layer composition change in the remelting alloying process.
Furthermore, the technological process and principle of the invention can also carry out alloying plating treatment on steel wires, structural members (such as section steel, channel steel and the like), steel plates, angle steel, round steel and other metal products, and the technological process or method improvement and the like which do not deviate from the essential connotation of the invention belong to the protection scope of the invention.
Further, the application fields of the alloyed plated steel bar include, but are not limited to, highways, bridges, tunnels, buildings, harbor facilities, etc.
Example 1
An alloyed plated steel bar and a preparation process and a method thereof specifically comprise the following steps:
paying off and straighter processing are carried out on the rolled steel bar (wire rod) with black oxide skin, then through-type shot blasting rust removal is carried out, clean steel bar with oxide skin removed is obtained, then spiral-flow water washing or air knife purging (for removing residual water stains or floating dust on the surface of the steel bar) is sequentially carried out, then the steel bar enters a sealed induction heating quartz tube filled with nitrogen and hydrogen for high-frequency induction heating, the heating frequency is 50kHz, the temperature of the surface of the steel bar reaches 700 ℃ (infrared thermometer for measuring the temperature), and the surface of the steel is activated; then horizontally penetrating molten zinc (wt% Zn is larger than or equal to 99%), plating a layer of molten zinc on the surface of the steel bar through the processes of mutual infiltration, diffusion growth and the like of a steel matrix and the molten zinc (450-470 ℃), then adopting nitrogen at 150-200 ℃ to carry out air knife wiping on the zinc layer, and removing the molten zinc attached to the surface of the steel bar so as to control the thickness of the attached molten zinc layer to be 30-50 mu m; spraying aluminum and magnesium mixed powder (Al: mg mass ratio is 6:3, spraying air is nitrogen) on the surface of the galvanized steel bar before the zinc liquid is solidified, simultaneously applying high-frequency induction heating to a quartz tube filled with nitrogen, enabling the sprayed aluminum and magnesium mixed powder to be rapidly melted and react with a zinc melting layer on the surface in a metallurgical way, enabling a coating to be alloyed, carrying out air knife blowing and water cooling, and passivating to obtain the zinc-aluminum-magnesium alloyed coated steel bar. After the surface of the steel bar is plated with a layer of molten zinc, the air knife is used for wiping test by adopting high-temperature nitrogen, so that the solidification of zinc liquid can be effectively prevented, the heat preservation effect is realized, and the possibility is provided for further alloying.
Example 2
An alloyed plated steel bar and a preparation process and a method thereof specifically comprise the following steps:
(1) Carrying out oil and rust removal treatment on the steel bars by adopting a laser cleaning machine, then enabling the cleaned steel bars to pass through a quartz tube filled with mixed protective gas of nitrogen and hydrogen, and simultaneously applying high-frequency induction heating with the frequency of 10kHz to keep the surface temperature of the steel bars at 550-650 ℃;
(2) The steel bar treated in the step (1) horizontally passes through a closed zinc melting device, the temperature of the zinc liquid is 450-480 ℃ (wt% Zn is larger than or equal to 99%), and the surface of the steel bar activated by nitrogen and hydrogen is utilized to carry out metallurgical diffusion reaction with the molten zinc liquid, so that a layer of molten zinc is attached to the surface of the steel bar;
(3) Blowing the zinc liquid by adopting a circular air knife to control the thickness of an attached molten zinc layer to be 30-50 mu m, then spraying proportioned zinc-aluminum-magnesium alloy powder (wherein Zn: al: mg=91:6:3) to the steel bar by passing through a quartz tube sealing device filled with nitrogen, and simultaneously applying high-frequency induction heating with the frequency range of 50-100 kHz; spraying powder and induction heating are carried out simultaneously, alloy powder sprayed on the surface of the steel bar is instantaneously melted, the alloy powder and molten zinc are subjected to metallurgical reaction, then nitrogen gas with the temperature of 35-100 ℃ is adopted for wiping, and the thickness of a coating is controlled to be 50-80 mu m; and then carrying out water cooling and passivation to obtain the alloyed coated steel bar with the surface layer of zinc, aluminum and magnesium and the middle layer of zinc or zinc-iron alloy, and then shearing and warehousing to finish the production of the whole alloyed coated steel bar.
Example 3
An alloyed plated steel bar and a preparation process and a method thereof specifically comprise the following steps:
(1) The concrete implementation process of the environment-friendly zinc plating for the steel bars is the same as that of the embodiment 2 (1) and (2), so that a layer of molten zinc is attached to the surfaces of the steel bars;
(2) Blowing the zinc liquid by using an annular air knife to control the thickness of an attached molten zinc layer to be 30-50 mu m, then spraying proportioned zinc-aluminum-magnesium alloy powder (Zn: al: mg=91:6:3) to the steel bar by passing through a quartz tube sealing device filled with nitrogen, applying medium-high frequency induction heating at the same time, enabling the frequency range to be 50-100kHz, enabling powder spraying and induction heating to be carried out simultaneously, enabling alloy powder sprayed on the surface of the steel bar to be instantaneously melted, enabling the alloy powder to carry out metallurgical reaction with molten zinc, then adopting nitrogen at room temperature to carry out gas wiping, controlling the thickness of a plating layer to be 50-80 mu m, and enabling the thickness of the plating layer after the alloy layer is sprayed to be larger than that of the environment-friendly zinc plating; then the wiped-off alloyed coated steel bar passes through a medium-high frequency induction heating coil again, the frequency range is 1-10 kHz, the temperature of the steel bar is controlled at 500-550 ℃, the alloyed coated steel bar and an iron matrix are subjected to diffusion reaction, then water cooling and passivation are carried out, the zinc-iron alloy coated steel bar rich in aluminum and magnesium elements is obtained, and then shearing and warehousing are carried out, so that the production of the whole alloyed coated steel bar is completed.
Example 4
An alloyed plated steel bar and a preparation process and a method thereof specifically comprise the following steps:
(1) After mechanical rust removal treatment is carried out by adopting a pass-through shot blasting rust remover, then a steel bar subjected to rotational flow water washing passes through a quartz tube, then a plating assistant agent is sprayed on the surface of the steel bar, and then the steel bar is heated to 80-150 ℃ by adopting power frequency (50 Hz) induction heating; covering the surface of the steel bar with a layer of plating assistant salt film;
(2) The steel bar treated in the step (1) horizontally passes through a closed zinc melting device, the temperature of zinc liquid is 450-480 ℃, and the passing time is 5-10 s, so that the surface of the steel bar is plated with a layer of molten zinc;
(3) And (3) blowing the zinc liquid by adopting an annular air knife, controlling the attaching thickness of the zinc layer to be 30-50 mu m, and spraying the proportioned Ni/Cr alloy powder (weight percent < 10%) on the steel bar in a quartz tube protected by airtight nitrogen before the zinc liquid is solidified.
(4) And (3) carrying out high-frequency (50-100 kHz) induction heating on the galvanized steel bar sprayed with alloy powder under the protection of nitrogen for 5-10 s to carry out remelting alloying, blowing by adopting an air knife, then rapidly cooling with water, passivating to obtain the zinc-chromium-nickel alloy coated steel bar rich in Ni/Cr alloy elements, and then shearing and warehousing to finish the production of the whole alloy coated steel bar.
The high-frequency induction heating is adopted to perform protection heating and remelting, so that the whole production process of the skin effect is not greatly influenced on the mechanical property index of the steel bar matrix material, and the influence of other heating modes on the whole performance of the steel bar is avoided.
The process and the principle can also be used for plating metal products such as steel wires, structural members (such as steel sections, channel steel and the like), steel plates, angle steel, round steel and the like, and the plating treatment belongs to the protection scope of the invention.
The present embodiment is merely illustrative of the spirit of the present invention, and those skilled in the art and studying the present invention will realize that the present invention is applicable to the prior art without departing from the scope of the present invention.

Claims (6)

1. A production process of an alloying coating steel bar is characterized in that: carrying out powder spraying alloying before molten zinc on the surface of the steel bar is solidified after the steel bar is hot galvanized, simultaneously applying high-frequency induction heating under the protection of inert gas, sweeping and water-cooling by a high-temperature air knife, controlling the zinc feeding amount, taking molten zinc on the surface of the steel bar as a solvent, taking sprayed alloy powder as a solute, keeping a coating in a molten state by inert gas protection induction heating, carrying out metallurgical reaction on the sprayed alloy powder and the molten zinc by using the skin effect of the high-frequency induction heating to alloy the coating, then sweeping and rapidly water-cooling by the air knife, forming an alloying coating layer with a certain thickness on the surface of the steel bar, namely obtaining gradient alloyed coated steel bar with zinc or zinc-iron alloy as a bottom layer to a surface layer, wherein metallurgical bonding is carried out between the coating layers;
the powder spraying and the high-frequency induction heating are simultaneously carried out, the alloy powder sprayed on the surface of the steel bar is instantaneously melted, the alloy powder and molten zinc are subjected to metallurgical reaction, metallurgical bonding between the alloy coating and the matrix is realized, the bonding force between the coating and the matrix and the compactness of the coating are obviously improved, the problem of cracking of a zinc layer in the bending process of the steel bar is avoided, and the completeness of the coating is ensured;
the high-frequency induction heating frequency is 50-200kHz, and the heating depth is 1-3mm;
the alloy powder is nanoscale powder;
the equipment system related in the production process mainly comprises a high-frequency induction heating system and a closed zinc melting device, wherein the closed zinc melting device comprises a working tank and a supply tank, the working tank is communicated with the lower part of the supply tank, the upper part of the working tank is closed, the upper part of the supply tank is communicated with the atmosphere, through holes for steel bars to enter and exit are formed in the upper parts of the working tank and the supply tank at the same height, and all the through holes are connected together sequentially through quartz pipes to form a channel for the steel bars to pass through; the working tank and the replenishing tank are respectively added with treatment liquid, and the liquid level of the working tank is higher than the position of the upper end of the through hole; the working tank and the replenishing tank are provided with heating systems,
the top of the working pool is in a sealed design and is provided with an air suction hole, the air suction hole is connected with a pressure control compensation system, the liquid level of the working pool is ensured to be higher than the upper end of the through hole during working, the automatic pressure compensation of the working pool is realized, and the pressure in the working pool is kept constant;
the intersection position of the supply tank and the working tank is provided with a communication hole, and the liquid level of the supply tank is higher than the upper side of the communication hole during working.
2. The process for producing an alloyed plated steel bar according to claim 1, wherein: after powder spraying, high-frequency induction heating, air knife blowing and water cooling, enabling the steel bars to pass through a medium-high frequency induction heating coil again, controlling the temperature at 550-560 ℃, and performing diffusion reaction on the alloy layer of the coated steel bars and the iron matrix; the frequency of the medium-high frequency induction heating is 1-50 kHz, the heating depth is not less than 10mm, and the preparation of the zinc-iron alloy layer after adding alloy elements is realized by adjusting the frequency range of the high-frequency and medium-high frequency induction heating.
3. The process for producing an alloyed plated steel bar according to claim 1, wherein: the hot galvanizing process is as follows:
the first scheme is as follows: passing the environment-friendly rust-removed steel bar through a closed tubular resistance furnace filled with inert gas or inert gas/hydrogen mixed gas, and then horizontally and rapidly passing through molten zinc liquid to plate a layer of zinc on the surface of the steel bar; the heating temperature of the resistance furnace is 450-700 ℃, and the temperature of the zinc liquid is 450-480 ℃;
the second scheme is as follows: passing the environment-friendly rust-removed steel bar through a closed ceramic tube or a quartz tube filled with inert gas or inert gas/hydrogen mixed gas, simultaneously applying high-frequency induction heating to enable the surface temperature of the steel bar to reach 500-800 ℃, and then horizontally and rapidly passing through molten zinc liquid to enable the surface of the steel bar to be plated with a layer of molten zinc;
third scheme: and (3) plating the environment-friendly rust-removed steel bar, and drying the steel bar, and then, entering molten zinc liquid to plate a layer of molten zinc on the surface of the steel bar.
4. A process for producing an alloyed plated steel bar according to claim 3, wherein: the high-temperature air knife is used for blowing nitrogen, the temperature of the nitrogen is 150-200 ℃, and the high-temperature air knife is used for removing zinc liquid attached to the surface of the steel bar to control the thickness of the attached molten zinc layer to be 30-50 mu m, and the uniformity is ensured.
5. A process for producing an alloyed plated steel bar according to claim 3, wherein: the environment-friendly rust removal is mainly at least one of mechanical rust removal, laser rust removal and environment-friendly rust remover rust removal, and the mechanical rust removal comprises shot blasting rust removal and steel brush rust removal.
6. The process for producing an alloyed plated steel bar according to any one of claims 1 to 5, wherein: the production process is also suitable for carrying out alloying plating treatment on metal products including steel wires, structural members, steel plates and round steel; the structural member comprises section steel, channel steel and angle steel.
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