CN109822064B - Method for growing inorganic coating on surface of copper plate of continuous casting crystallizer - Google Patents
Method for growing inorganic coating on surface of copper plate of continuous casting crystallizer Download PDFInfo
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Abstract
The invention provides a method for growing an inorganic coating on the surface of a copper plate of a continuous casting crystallizer, which comprises the following steps: 1) preparing a seed crystal synthetic solution, and reacting to obtain seed crystals; 2) dissolving seed crystals in a solvent to prepare an electrophoresis liquid crystal, placing a copper plate in the electrophoresis liquid crystal, performing electrophoresis to enable the seed crystals to be adsorbed to partial or all areas on the surface of the copper plate, and performing seed crystal treatment; 3) and (3) carrying out heat treatment on the copper plate after the crystal seeding, then putting the copper plate into secondary synthetic liquid for secondary growth, so that a high-strength corrosion-resistant wear-resistant high-temperature-resistant inorganic coating is formed on part or all of the surface of the copper plate. Aiming at the defects of the common electroplating and thermal spraying coatings of the continuous casting crystallizer copper plate at present, a layer of inorganic coating which has good bonding force with a matrix, high temperature abrasion resistance, corrosion resistance and good thermal conductivity is prepared on the whole or partial area of the surface of the continuous casting crystallizer copper plate so as to prolong the service life of the continuous casting crystallizer copper plate.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for growing a high-strength wear-resistant corrosion-resistant high-temperature-resistant inorganic coating on the surface of a copper plate of a continuous casting crystallizer.
Background
In the continuous casting production of metals, a crystallizer is the heart of a continuous casting machine, and the performance and the service life of the crystallizer directly influence the operating rate and the quality of a casting blank in the continuous casting production and influence the cost of a continuous casting process. The working environment of the crystallizer is quite harsh: the outer surface of the shell is contacted with cooling water at the temperature of 30-40 ℃, and the inner surface of the shell is contacted with molten slag and molten metal (or a high-temperature metal blank shell), so that thermal fatigue, high-temperature oxidation and chemical corrosion are easily caused; the crystallizer also bears mechanical stress such as hydrostatic pressure of metal liquid and friction force of a casting blank shell, which are easy to cause abrasion and scratch, for a long time; in addition, the on-line width adjustment and taper adjustment of the crystallizer can also cause scratch of the inner wall of the crystallizer. Therefore, the working environment of the crystallizer seriously influences the working life of the crystallizer.
With the continuous development of continuous casting technology and the continuous development of new continuous casting technology, the continuous casting production is developed to high drawing speed, high quality and high productivity, the working conditions of a continuous casting crystallizer are more and more rigorous, and the requirement on the crystallizer is higher and higher. Wherein the high temperature wear resistance of the crystallizer coating is an important factor influencing the continuous casting development. At present, in the continuous casting production, a Ni or Ni-Co and Ni-Cr alloy coating is prepared on the surface of a crystallizer copper plate by adopting an electroplating or thermal spraying method so as to improve the high-temperature wear resistance of the crystallizer copper plate and prevent matrix copper from permeating into a cast body. For electroplating Ni or Ni-Co alloy, because the electroplating method is simple and easy to control, the method is a surface treatment method commonly adopted in the field of domestic and foreign continuous casting at present, but the coating prepared by the electroplating method is combined with a matrix mechanically, not metallurgically, and the electroplated layer is easy to peel off and separate under the working environment of continuous thermal stress and mechanical stress, and the electroplated layer inevitably has pinholes in the electroplating process, so that the oxidation resistance of the electroplated layer is not favorable; for thermal spraying, the coating has the advantages of wear resistance, corrosion resistance, high deposition rate and the like, but a workpiece is easy to generate thermal stress in the thermal spraying process, so that the workpiece is deformed, and the subsequent lengthy thermal treatment needs to be carried out on the workpiece.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a method for growing a high-strength wear-resistant corrosion-resistant high-temperature-resistant inorganic coating on the surface of a copper plate of a continuous casting mold, which is used to solve the problems of poor hardness, poor wear resistance, poor corrosion resistance and poor high-temperature resistance of the inorganic coating on the surface of the copper plate of the continuous casting mold in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a method for growing a high-strength wear-resistant corrosion-resistant high-temperature-resistant inorganic coating on the surface of a copper plate of a continuous casting crystallizer, comprising the following steps:
1) preparing a seed crystal synthetic solution, and reacting to obtain seed crystals;
2) dissolving the seed crystal in a solvent to prepare an electrophoresis liquid crystal, placing the copper plate in the electrophoresis liquid crystal, performing electrophoresis to enable the seed crystal to be adsorbed to partial or all areas on the surface of the copper plate, and performing seed crystal treatment;
3) and (3) carrying out heat treatment on the copper plate after the crystal seeding, then putting the copper plate into secondary synthetic liquid for secondary growth, so that a high-strength corrosion-resistant wear-resistant high-temperature-resistant inorganic coating is formed on part or all of the surface of the copper plate.
Optionally, in the step 1), by mol, the ratio of ethyl orthosilicate in the seed crystal synthesis solution is: tetrapropylammonium bromide (or tetrapropylammonium hydroxide): sodium hydroxide: water 1: (0.05-1): (0.01-0.13): (10-120), preferably 1: (0.1-0.8): (0.04-0.13): (20-80).
Optionally, in the step 1), when the seed crystal is prepared, the reaction temperature is 50-150 ℃, and preferably 70-120 ℃.
Optionally, in the step 1), when the seed crystal is prepared, the reaction time is 10-100 hours, and preferably 30-80 hours.
Optionally, in the step 2), the solvent of the electrophoretic liquid crystal is an organic solvent.
Optionally, in the step 2), the organic solvent is selected from isopropanol.
Optionally, in the step 2), the concentration of the electrophoretic liquid crystal is 3-50 g/L, and specifically may be 5g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 45g/L, 50g/L, and the like.
Optionally, in the step 2), the pH of the electrophoretic liquid crystal is adjusted to 2-6, which may be 2.5, 3, 3.5, 4, 5, 6, and the like.
Optionally, in the step 2), during electrophoresis, the copper plate is used as a cathode, the inert electrode is used as an anode, and the electrolyte is the electrophoretic liquid crystal.
Optionally, in step 2), the inert electrode is a graphite electrode.
Optionally, in the step 2), the electrophoresis voltage is 1.5-60 v, and the electrophoresis time is 0.2-3 h.
Optionally, in the step 2), the electrophoresis voltage is 3-30 v, and the electrophoresis time is 1-2 h.
Optionally, in the step 2), after the electrophoresis seeding is finished, the surface of the copper plate is washed to be neutral, and then heated to 60-200 ℃, and the temperature is kept for 0.5-5 h, preferably 100-200 ℃, and the temperature is kept for 1-3 h.
Optionally, in the step 2), the heating is performed under vacuum or under protection of a protective gas.
Optionally, in the step 2), the protective gas is at least one selected from hydrogen, nitrogen and argon.
Optionally, in the step 3), by mol, the ratio of ethyl orthosilicate in the secondary synthetic liquid: tetrapropylammonium bromide (or tetrapropylammonium hydroxide): sodium hydroxide: water 1: (0.15-0.8): (0.13-0.85): (30-150), preferably 1: (0.2-0.5): (0.25-0.6): (60-100).
Optionally, in the step 3), during the secondary growth, the reaction temperature is 100 to 200 ℃, and preferably 130 to 180 ℃.
Optionally, in the step 3), the heat preservation time is 2-72 hours, preferably 6-48 hours, during the secondary growth.
Optionally, in the step 3), after the growth is finished, drying is performed, so that a high-strength, corrosion-resistant, wear-resistant and high-temperature-resistant inorganic coating is formed on a part or all of the surface of the copper plate.
Optionally, in the step 3), the drying temperature is 50-120 ℃.
Optionally, in the step 3), the drying time is 2-8 h.
The invention also provides a synthetic liquid for growing the high-strength wear-resistant corrosion-resistant high-temperature-resistant inorganic coating on the surface of the copper plate of the continuous casting crystallizer, which comprises a seed crystal synthetic liquid, wherein in terms of mole, the seed crystal synthetic liquid contains tetraethoxysilane: tetrapropylammonium bromide (or tetrapropylammonium hydroxide): sodium hydroxide: water 1: (0.05-1): (0.01-0.13): (10-120), preferably 1: (0.1-0.8): (0.04-0.13): (20-80).
Optionally, the electrophoresis device further comprises an electrophoresis synthetic liquid, and the solute of the electrophoresis synthetic liquid is an organic solute.
Optionally, the organic solute is selected from isopropanol.
Optionally, the concentration of the electrophoretic liquid crystal is 3-50 g/L.
Optionally, the pH of the electrophoretic liquid crystal is 2-6.
Optionally, the method further comprises a second synthetic liquid, wherein the molar ratio of ethyl orthosilicate: tetrapropylammonium bromide (or tetrapropylammonium hydroxide): sodium hydroxide: water 1 (0.15-0.8): (0.13-0.85): 30-150), preferably 1: (0.2-0.5): (0.25-0.6): (60-100).
As described above, the method for growing the inorganic coating on the surface of the copper plate of the continuous casting mold of the invention has the following beneficial effects: aiming at the defects of the common electroplating and thermal spraying coatings of the continuous casting crystallizer copper plate at present, a layer of inorganic coating which has good bonding force with a matrix, high temperature abrasion resistance, corrosion resistance and good thermal conductivity is prepared on the whole or partial area of the surface of the continuous casting crystallizer copper plate so as to prolong the service life of the continuous casting crystallizer copper plate.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
A kind of hydrothermally synthesized corrosion-resistant, wear-resistant and high-temperature-resistant inorganic coating (such as all-silicon Silicate-1 type zeolite coating) can meet the requirements of continuous casting process on crystallizer copper plate coating. The main structure of the inorganic coating is mainly Si-O, so that the continuous casting molten metal and the casting blank are not polluted. The inorganic coating can be combined with the substrate copper by Cu-O-Si chemical bonds, so that the binding force between the coating and the substrate is good. In addition, such coatings have good high temperature wear resistance and good thermal conductivity. Different from a thermal spraying process, the hydrothermal method has the advantages that the reaction temperature for preparing the inorganic coating on the surface of the substrate copper is lower (less than 200 ℃), the deformation of the substrate copper plate is not caused, the residual stress of the substrate copper plate is released, and the shape and the size of the substrate copper plate are stabilized. Therefore, the inorganic coating has great application prospect for the surface modification and reinforcement of the crystallizer copper plate.
In the invention, the inorganic coating is prepared on the surface of the crystallizer copper plate by adopting a mode of growing a film through electrophoretic crystal twice hydrothermal synthesis in order to ensure that the coating is uniform and compact by considering the larger size of the crystallizer copper plate.
The crystallizer copper plate coating is an inorganic coating with a Si-O structure, and the preparation of an all-silicon Silicate-1 zeolite coating on matrix copper is selected for description in the embodiment, and the specific preparation steps are as follows:
(1) pretreatment of base copper plate
Carrying out sand blasting and coarsening treatment on the matrix copper plate by adopting quartz sand with the granularity of 18 meshes; then cleaning for 10min at 70 ℃ by using alkaline degreasing fluid, wherein the alkaline degreasing fluid comprises the following components: 10g/L NaOH, 50g/L Na2CO3、60g/L Na3PO43g/L OP-10 emulsifier, then removing soap scum generated on the surface by hot water washing, and washing away residues on the surface by cold water; and then carrying out acid washing activation treatment on the matrix copper plate for about 1min by adopting an HCl solution with the concentration of 5 wt%, and then washing away the residual acid liquor on the surface of the matrix by using cold water.
(2) Seed preparation
According to the molar ratio of ethyl orthosilicate: tetrapropylammonium bromide (or tetrapropylammonium hydroxide): sodium hydroxide: water 1: 0.5: 0.1: 70, and completely hydrolyzing the seed crystal synthesis solution under stirring. Pouring the synthetic solution after hydrolysis into the inner cavity of a container of a hydrothermal reaction kettle, and preserving heat for 60 hours at 110 ℃; and centrifuging and filtering the seed crystal synthetic solution after the reaction is finished, separating the nano zeolite particle seed crystal, washing the seed crystal particle with distilled water until the pH value is neutral, and drying the seed crystal particle at 60 ℃ for later use.
(3) Preparation of electrophoretic liquid crystal
Adopting isopropanol as a solvent, taking the crystal seed prepared in the step (2) as a solute, preparing an electrophoresis liquid crystal with the concentration of 20g/L, adjusting the pH of the electrophoresis liquid crystal to 3.5 by adopting HCl, taking a pretreated matrix copper plate as a cathode, taking a graphite electrode as an anode, taking an electrolyte as the prepared liquid crystal, and setting the electrophoresis voltage to 15V and the electrophoresis time to 0.5 h; after the electrophoresis seeding is finished, the surface of the copper plate is washed to be neutral, and then the copper plate is put into a heating furnace to be heated to 160 ℃ under vacuum, and the temperature is kept for 2 h.
(4) Crystal seed secondary growth film formation
According to the molar ratio of ethyl orthosilicate: tetrapropylammonium bromide (or tetrapropylammonium hydroxide): sodium hydroxide: water 1: 0.35: 0.5: 80, and completely hydrolyzing the secondary synthetic liquid under stirring. Pouring the synthetic solution after hydrolysis into the inner cavity of the hydrothermal reaction kettle, then putting the part or all of the copper plate after seed crystal treatment into the secondary synthetic solution, and preserving heat at 130 ℃ for 24 hours to form a film. And then, washing the copper plate by water to remove residual synthetic liquid on the surface, putting the copper plate into a drying oven at 100 ℃ for heat preservation for 6 hours to realize drying, so that a high-strength, corrosion-resistant, wear-resistant and high-temperature-resistant inorganic coating is formed on part or all of the surface of the substrate copper plate.
Comparison of coating Properties
The inorganic coating prepared in the example is compared with the pure Ni and Ni-Co electroplated coating on the surface of the traditional crystallizer by detection, and the result is as follows:
TABLE 1
Wherein the test experimental conditions are respectively as follows:
1) vickers microhardness: loading 50gf, and keeping the load for 15 s;
2) and (3) reciprocating friction: a silicon carbide ceramic ball friction pair with the diameter of 6mm is added with 15N, and the friction time is 60 min;
3) corrosion current density (polarization curve): the potentiodynamic scanning speed is 1 mV/s.
As can be seen from the above table, the pure silica type zeolite coating has higher hardness, lower friction coefficient and smaller corrosion current density compared with the traditional pure nickel and nickel-cobalt plating of the crystallizer, i.e. the pure silica type zeolite inorganic coating has better wear resistance and corrosion resistance compared with the traditional pure nickel and nickel-cobalt plating.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (4)
1. A method for growing a high-strength wear-resistant corrosion-resistant high-temperature-resistant inorganic coating on the surface of a copper plate of a continuous casting crystallizer is characterized by comprising the following steps of:
1) preparing a seed crystal synthetic solution, and reacting to obtain seed crystals: according to the molar ratio of ethyl orthosilicate: tetrapropylammonium bromide or tetrapropylammonium hydroxide: sodium hydroxide: water =1: (0.05-1): (0.01-0.13): (10-120) preparing a seed crystal synthetic liquid according to the proportion, completely hydrolyzing the seed crystal synthetic liquid under the stirring condition, pouring the synthetic liquid after hydrolysis into an inner cavity of a container of a hydrothermal reaction kettle, preserving heat at 50-150 ℃ for 10-100 h, centrifuging and filtering the seed crystal synthetic liquid after reaction is finished, separating out nano zeolite particle seed crystals, washing the seed crystal particles with distilled water until the pH value is neutral, and drying the seed crystals at 60 ℃ for later use;
2) dissolving the seed crystal in isopropanol to prepare an electrophoresis liquid crystal with the concentration of 3-50 g/L, and adjusting the pH of the electrophoresis liquid crystal to 2-6; placing a copper plate in the electrophoresis liquid crystal, taking the copper plate as a cathode, taking an inert electrode as an anode and taking the electrophoresis liquid crystal as an electrolyte, carrying out electrophoresis, wherein the electrophoresis voltage is 1.5-60 v, the electrophoresis time is 0.2-3 h, and adsorbing the seed crystal to partial or all areas on the surface of the copper plate to carry out seed crystal treatment; after the electrophoresis seeding is finished, washing the surface of the copper plate to be neutral, heating the copper plate to 60-200 ℃, and preserving heat for 0.5-5 h;
3) according to the molar ratio of ethyl orthosilicate: tetrapropylammonium bromide or tetrapropylammonium hydroxide: sodium hydroxide: and (2) preparing a secondary synthetic solution from water =1 (0.15-0.8) to (0.13-0.85) to (30-150), completely hydrolyzing the secondary synthetic solution under stirring, pouring the hydrolyzed secondary synthetic solution into an inner cavity of a hydrothermal reaction kettle, putting part or all of the seeded copper plate into the secondary synthetic solution, preserving heat at 100-200 ℃ for 2-72 hours, carrying out secondary growth, and drying after the growth is finished, so that a high-strength, corrosion-resistant, wear-resistant and high-temperature-resistant inorganic coating is formed on part or all of the surface of the copper plate.
2. The method of claim 1, wherein: in the step 1), by mol, the crystal seed synthetic liquid contains tetraethoxysilane: tetrapropylammonium bromide or tetrapropylammonium hydroxide: sodium hydroxide: water =1: (0.1-0.8): (0.04-0.13): (20-80).
3. The method of claim 1, wherein: in the step 2), heating is carried out under the protection of vacuum or protective gas.
4. The method of claim 1, wherein: in the step 3), the drying temperature is 50-120 ℃;
and/or, in the step 3), the drying time is 2-8 h.
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| US5014768A (en) * | 1989-06-30 | 1991-05-14 | Waters & Associates | Chill plate having high heat conductivity and wear resistance |
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| CN101994147B (en) * | 2009-08-12 | 2012-09-05 | 比亚迪股份有限公司 | Surface treatment method of metal base materials |
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| CN103014794B (en) * | 2011-09-23 | 2015-06-24 | 上海宝钢工业技术服务有限公司 | Preparation method of composite coating on crystallizer copper plate surface |
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