CN112848552A - Copper-steel solid-liquid composite bimetallic material for ocean engineering and preparation method thereof - Google Patents
Copper-steel solid-liquid composite bimetallic material for ocean engineering and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D19/00—Casting in, on, or around objects which form part of the product
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B2001/225—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length by hot-rolling
Abstract
The invention provides a copper-steel solid-liquid composite bimetal material for ocean engineering and a preparation method thereof, wherein a base plate in the bimetal composite material is a steel plate, and a copper alloy plate is attached to the surface of the steel plate; the ratio of the thickness of the copper alloy to the thickness of the steel slab is 1: (5.6-11.2), the preparation method comprises the steps of steel plate pretreatment, preheating, solid-liquid compounding, composite plate blank heating, hot rolling, straightening and heat treatment; the copper-steel bimetal composite material produced by the method has the cross-section Vickers hardness of 192-208 HV, the cross-section hardness difference of less than or equal to 16HV, the Z-direction tensile strength Rm of more than or equal to 440MPa, the elongation A of more than or equal to 25 percent, the composite interface shear strength of 240-260 MPa, qualified bending test and good seawater corrosion resistance.
Description
Technical Field
The invention belongs to the field of metal material production, and particularly relates to a copper-steel solid-liquid composite bimetallic material for ocean engineering and a preparation method thereof.
Background
The sea is the most corrosive environment and is a complex consisting of seawater containing 3% NaCl, dissolved gas, suspended solids, organic matters and organisms. Carbon steel in a plurality of materials has poor seawater corrosion resistance, and stainless steel can generate gaps, stress and pitting corrosion; among metal materials, copper alloy has excellent seawater corrosion resistance and oxide growth resistance, but has high cost. Therefore, the development of the copper-steel composite material not only can exert the performance advantages of the respective component materials, but also can realize the performance advantage complementation between the component materials, meet the performance requirements which can not be met by a single metal material, save the precious metal material and have higher economic benefit and social benefit.
Some experts and scholars at home and abroad are dedicated to the research of copper-steel bimetal, on one hand, the use of noble metal Cu is reduced, and on the other hand, the performance of the composite material is improved.
In the technical scheme provided by the invention with application number 200910044854.9, namely the Bi bronze-Steel composite bimetallic bearing material and the manufacturing method thereof, the material base layer adopts carbon steel as the material, the surface layer is Bi bronze alloy, and the Bi bronze alloy is sintered on the surface of the carbon steel. The bismuth bronze alloy is sintered on the surface of the carbon steel material by adopting the principle of a powder metallurgy sintering method. The disadvantages of the method are that the sintered bimetallic composite material has large porosity, poor mechanical property, poor bearing capacity and impact resistance and short service life.
The invention with application number of 200910162920.2, namely the copper-steel composite material and the preparation method thereof, discloses a technical scheme that the composite material comprises the following chemical components in percentage by weight: 10-15% of Cu and 85-90% of steel, and the structure is that copper and steel are compounded into a whole. After surface treatment is carried out on copper and a steel strip, the copper and the steel strip are rolled into a high-precision steel strip and a high-precision copper strip through cold rolling; after surface cleaning, removing surface residues, degreasing, rolling into a high-precision copper-steel composite belt by a cold rolling mill, and annealing. The method has the disadvantages of low production efficiency, low success rate and easy layering of products by adopting a cold rolling and rolling composite method.
In the invention 'isothermal welding method for producing copper-steel composite material' with application number of 01107029.3, firstly, a protective agent is added into a gap between a steel core rod and an outer wall of a composite blank without the steel core rod, and then electrolytic copper is added into a hopper of the composite blank; and (3) putting the fed composite blank into a well-type electric furnace which is heated to 1130-1150 ℃, and after the electrolytic copper is completely melted, powering off the electric furnace section by section from the bottom to sequentially cool the composite blank from the bottom to the top. It has the disadvantages that the production of bimetallic composites is limited by production equipment, limited in size, and cannot be mass produced.
The invention discloses an induction casting connection method of a copper-steel composite component with application number 200910306947.4, which solves the problems of poor air tightness of a workpiece after welding and low tensile strength of a joint in the existing brazing method. The tensile strength of the composite member can reach 232MPa by adopting an induction casting method, but the application has limitation, and the product is only used for connecting the copper-steel composite member.
The invention 'a production method of copper-steel composite plates' with application number 201210188109.3 adopts the steps of surface cleaning, roughening treatment, bonding layer spraying, rolling, annealing, flattening, polishing and the like to produce the bimetal composite material, and has the defects that the method has higher requirements on the roughness of the surfaces of steel and copper, and the bonding layer needs to be sprayed, so that the process is complicated, the production efficiency is low, and the bonding interface is easy to cause non-uniformity.
In the invention 'a welding type copper-steel composite cooling wall manufacturing method' with application number of 201710630328.5, the copper plate and the steel plate are pretreated firstly: cutting, derusting, polishing, leveling and bending, then, under the conditions of inert environment, high temperature and high pressure, enabling the copper plate and the pretreated plate surface of the steel plate to be opposite, rolling while tracking and welding to form a copper-steel composite cooling wall blank, and finally, carrying out subsequent processing. The method has the disadvantages that the welding is carried out while rolling, the difficulty is high, the synchronous operation in large-scale production is difficult, and the implementation is difficult.
Disclosure of Invention
The invention aims to overcome the problems and the defects and provide a copper-steel solid-liquid composite bimetallic material for ocean engineering and a preparation method thereof, wherein the copper-steel solid-liquid composite bimetallic material has the advantages of high cost and usability, high seawater corrosion resistance, high strength and hardness, higher shear strength and high production flow.
The purpose of the invention is realized as follows:
a copper-steel solid-liquid composite bimetal material for ocean engineering is characterized in that a base plate in the bimetal composite material is a steel plate, and a copper alloy plate is attached to the surface of the steel plate; the copper alloy comprises the following components in percentage by weight: ni: 15.0% -25.0%, Zn: 5.0% -10.0%, Sn: 0.5% -1.0%, Si: 2.0% -3.0%, Mn: 0.5% -1.3%, Fe: 1.0-1.5 percent, and the balance of Cu and inevitable impurities; the steel comprises the following components in percentage by weight: c: 0.07 to 0.15%, Si: 0.15-0.25%, Mn: 1.30-1.40%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, Cr: 0.10% -0.20%, V: 0.05-0.10%, Mo: 0.02% -0.08%, B: 0.002% -0.003%, and the balance of Fe and inevitable impurities.
The bimetal composite material is formed by compounding a copper alloy plate and a base plate steel plate, wherein the thickness ratio of the copper alloy plate to the base plate steel plate is 1: (5.6-11.2) and the copper alloy plate is attached to one surface or both surfaces of the steel plate.
The composite material has the section hardness of 192-208 HV, the section hardness difference of less than or equal to 16HV, the Z-direction tensile strength Rm of more than or equal to 440MPa, the elongation A of more than or equal to 25 percent and the composite interface shear strength of 240-260 MPa.
The copper alloy of the invention has the following design reasons:
ni: in the invention, Ni has the effects of improving the strength and toughness of the alloy and resisting stress corrosion cracking, and simultaneously can improve the processing performance of the alloy, and improve the corrosion-resistant fatigue performance, corrosion resistance, cavitation corrosion resistance, marine organism fouling resistance and other performances of the alloy, and under the combined action of other alloy elements, the invention can achieve the corrosion-resistant effect of B30 alloy and simultaneously reduce the cost, so that the invention selects to add Ni: 15.0 to 25.0 percent.
Zn: the plasticity of the alpha solid solution of the copper alloy is improved, and the alloy strength is continuously improved along with the increase of the Zn content. However, the plasticity of the material is affected by the excessively high Zn content, so that the invention selects to add Zn: 5.0 to 10.0 percent.
Sn: the addition of Sn in the invention can not only improve the mechanical property of the copper alloy, but also inhibit the removal of Zn from the copper alloy and enhance the corrosion resistance of the copper alloy. In the invention, proper amount of Sn and Ni are added simultaneously, so that on one hand, the strength and hardness can be improved, better elastic property can be obtained, and the cost is saved to a great extent in the preparation process. Therefore, the invention selects to add Sn: 0.5 to 1.0 percent.
Si: in the copper alloy, the strength can be improved by adding a proper amount of Si without losing the corrosion resistance, so that the invention selects and adds Si: 2.0 to 3.0 percent.
Mn: in the invention, proper amount of Mn plays a role in solid solution strengthening, and the alloy strength is improved without reducing the plasticity, so that the Mn content is 0.5-1.3%.
Fe: the addition of proper amount of Fe is favorable for grain refinement and the generation of metal compounds with Ni, which is favorable for improving the erosion corrosion resistance of the alloy. However, if the content of Fe is too high, brittle compounds are likely to appear on the grain boundary, which lowers the corrosion potential and affects the corrosion resistance of the alloy. Therefore, in the present invention, Fe: 1.0 to 1.5 percent.
The composition design reasons of the steel of the present invention are as follows:
c: in the present invention, a part of carbon in the steel enters into the matrix of the steel to cause solid solution strengthening, and another part of carbon combines with carbide-forming elements in the alloying elements to form alloyed carbides, so that it greatly affects strength, ductility and weldability. However, the C content is too high to form carbide with Cr, which causes the corrosion resistance in steel to be reduced and influences the performance of resisting the carbonization corrosion, so the C content is selected to be 0.07-0.15 percent.
Si: silicon is one of important elements for strengthening ferrite, and can obviously improve the strength and hardness of steel and improve the hardenability. When in a strong oxidizing medium, Si can improve the corrosion resistance of steel, and research shows that Si has good Cl resistance like Mo-The higher the Si content in the steel, the more positive the pitting potential, the less susceptible to corrosion. However, the excessive amount of Si makes the spheroidized carbide particles larger in diameter and larger in spacing, and promotes segregation to cause formation of a banded structure, so that the transverse properties are lower than those in the longitudinal direction, therefore, the Si content is selected to be 0.15-0.25%.
Mn: the Mn-containing steel is a solid solution strengthening element in the steel, the crystal grains are refined, the ductile-brittle transition temperature is reduced, the hardenability is improved, and the Mn-containing steel can change the property and the shape of an oxide formed during the solidification of the steel. Meanwhile, the material has larger affinity with S, and can avoid forming low-melting-point sulfide FeS on a crystal boundary. However, the plasticity of the steel is affected by the excessively high content, so that the Mn content is selected to be 1.30-1.40 percent.
P, S: s is distributed in the steel in the form of MnS, and the MnS extends along the rolling direction in the hot rolling process, so that the transverse mechanical property of the sulfur free-cutting steel is obviously reduced, and the anisotropy of the steel is enhanced. Meanwhile, S is harmful to the corrosion resistance of the die steel, so that the welding performance is deteriorated. Although P can increase ferrite hardness in a proper amount and improve the surface finish and machinability of parts, too high P in steel increases cold brittleness, and too much S, P affects the homogeneity and purity of the steel. Therefore, P is less than or equal to 0.015 percent and S is less than or equal to 0.015 percent are selectively added.
Cr: cr can improve the hardenability of the iron-chromium alloy, passivate steel and endow the steel with good corrosion resistance and rust resistance, the corrosion potential of Cr is more negative than that of iron, the passivating capability is stronger than that of iron, and in the iron-chromium alloy, the increase of the Cr content can cause the corrosion potential and the critical passivation potential of the alloy to move towards the direction of negative potential. Therefore, the content of the Cr added is 0.10 to 0.20 percent.
V: v in the Steel of the invention is V4C3The isocarbides exist stably, the movement of grain boundaries and the grain growth in the steel are generally inhibited in a fine particle state, a part C, N in the steel is fixed, the content of ferrite and pearlite in the steel is directly influenced, and the distribution and the form of ferrite are changed. The V dissolved in the austenite can improve the stability of the super-cooled austenite, reduce the transformation temperature, reduce the pearlite colony, fragment the pearlite and reduce the inter-lamellar spacing. The grain can be effectively refined by adding V, and the fine grain strengthening effect is achieved, so that the content of the added V is 0.05-0.10%.
Mo: mo can improve the hardenability of steel, form special carbide in the steel and improve the heat treatment stability of the steel. Mo is one of the most effective elements for improving the pitting corrosion resistance of the steel, and MoO is used as the Mo element4 2-Form of (2) dissolves and adsorbs on the metal surface to form a protective film, inhibiting Cl-To prevent Cl-The pitting corrosion resistance is improved by increasing the pitting potential and decreasing the pitting corrosion rate, but too much Mo content promotes the formation of δ ferrite, resulting in adverse effects. Therefore, the content of Mo added in the invention is 0.02-0.08%.
B: since the ratio of the atomic radius of B to that of Fe is 0.79, boron atoms cause large distortion energy regardless of whether they form an interstitial solid solution or a solid solution with iron. Therefore, B is easy to be segregated in the austenite crystal boundary, energy at the crystal boundary is reduced due to the fact that part of crystal boundary defects are filled, fluctuation of energy at the crystal boundary is reduced, diffusion of carbon atoms at the crystal boundary is hindered, nucleation of a new phase at the austenite crystal boundary is difficult during austenite decomposition, so that the incubation period of austenite decomposition is prolonged, nucleation of pro-eutectoid ferrite at the austenite crystal boundary is inhibited, hardenability is improved, and the full-thickness strength of steel for ocean engineering is guaranteed. However, if the content of B is too high, strong segregation tends to occur in the grain boundary, an enrichment zone with a certain width is formed, a carbide precipitation phase is formed, stress concentration is easily caused in the deformation process, the carbide also provides a continuous expansion path and is cleaved and broken, and meanwhile, excessive precipitation of B also has a certain influence on the toughness. Therefore, the content of the B added is 0.002% -0.003%.
The second technical scheme of the invention provides a preparation method of a copper-steel solid-liquid composite bimetallic material for ocean engineering, which comprises the steps of steel plate pretreatment, preheating, solid-liquid compounding, composite plate blank heating, hot rolling, straightening and heat treatment;
(1) pretreatment of a steel plate: firstly, milling a groove on the surface of a steel plate, wherein the depth of the groove is 5-8 mm, mechanically polishing, pickling, washing and drying the surface of the groove to polish rust on the surface of the groove to expose a bright fresh metal surface, and simultaneously roughening and roughening the surface of the steel plate, so that the effective contact area between a copper alloy and a base steel plate is greatly increased, and the mechanical property of a transition interface of a composite material is favorably improved. And then degreasing the steel plate, heating the degreasing solution to 60-70 ℃ to degrease the surface of the steel plate in order to effectively remove oil stains on the surface of the steel plate, then cleaning the steel plate by acetone, coating an antioxidant, and drying the steel plate for later use.
(2) Preheating: heating the pretreated steel plate to 850-900 ℃, and then placing the steel plate in a graphite mold cavity. The steel plate is preheated to ensure that a certain heat volume ratio exists between the liquid copper alloy and the solid steel plate in the pouring process of the copper alloy, and because the copper alloy and the steel plate can generate element diffusion phenomenon in the compounding process, the higher preheating temperature can improve the diffusion reaction condition in the compounding process of the copper alloy and the matrix steel plate, so that atoms at the interface joint part have enough energy to carry out mutual diffusion. Preferably, the preheating process is under inert gas or vacuum protection.
(3) Solid-liquid compounding: filling the graphite mold cavity with inert gas before casting, so as to reduce oxygen content and oxidation; then, rapidly pouring the smelted copper alloy molten metal onto the surface of the pretreated steel plate, wherein the pouring temperature is 1150-1200 ℃, then air-cooling, and air-cooling until the side temperature of the copper alloy is 950-980 ℃; and taking out the cast blank, immediately spraying cooling water on the bottom of the steel plate for cooling until the cast blank is cooled to 200-250 ℃, immediately coating an antioxidant on the side of the copper alloy to prevent the copper alloy from being oxidized, then air-cooling to room temperature, and performing subsequent machining to obtain the copper alloy/steel bimetal composite plate blank. The thickness of the copper alloy slab in the bimetal composite slab is 5-8 mm, and the ratio of the thickness of the copper alloy slab to the thickness of the steel slab is 1: (5-10).
According to the thickness requirement, on one hand, according to the flowing deformation behavior of the copper-steel bimetal, more uniform metal flowing is obtained in the subsequent rolling process; on one hand, the use requirement of the steel for ocean engineering is met, the excellent seawater corrosion resistance and the anti-oxide growth capacity of the copper alloy are exerted, and the copper alloy which is a precious metal material is saved, so that the method has higher economic benefit and social benefit.
The temperature plays a main role in promoting atomic diffusion, the higher the temperature is, the more violent the thermal motion of the atoms is, the higher the probability that the atoms are activated to migrate under the action of a high-temperature heat source is, and the atoms can obtain enough energy in a short time under the high-temperature state and deviate from the equilibrium position to migrate. The invention adopts higher copper alloy casting temperature, increases the number of atoms deviating from equilibrium positions, increases the bonding probability among the atoms, rapidly increases the effective bonding points of the interface, increases the width of the composite interface of the plate blank, and increases the bonding strength of the interface.
According to the invention, the bimetal composite blank is cooled in sections after casting, so that on one hand, the slow cooling speed of the copper alloy and the steel plate after casting and compounding is prevented, the bimetal composite blank is in a high-temperature section for a long time, crystal grains grow up, and adverse effects on the shearing strength and the tensile strength of the material are avoided, on the other hand, the cooling speed is increased to reduce oxidation, the generation of oxides at the joint surface of the composite plate blank is reduced, the production efficiency is improved, and the preparation period of the composite material is shortened.
(4) Heating the composite plate blank: because the melting points of the copper alloy and the steel are greatly different, the hot rolling temperature of the steel is almost close to the melting temperature of the copper alloy, so the rolling heating temperature is reasonably selected. The heating temperature of the slab is controlled to be 910-960 ℃, and the soaking section is insulated for 2-3 h. Preferably, the composite plate heating process is under inert gas protection or vacuum protection.
(5) Hot rolling: because the thermal expansion coefficients and the elongation rates of the steel and the copper alloy are different, the rolling reduction is reasonably determined so as to ensure the composite strength and the equipment safety. The rolling temperature is 800-850 ℃, the hot rolling temperature of the invention is controlled to be higher than the recrystallization temperature of the copper alloy with lower melting point, the first pass controlled reduction rate is 15-17%, the comprehensive action of the thickness ratio, the thermal deformation temperature and the reduction rate of the copper/steel plate blank has larger influence on the flow difference of the bimetal composite material, the combination interface can be flat and straight by adopting the thickness ratio, the hot rolling temperature and the larger first pass reduction rate, the mutual diffusion of intermetallic elements at two sides is increased, the diffusion distance is larger, the diffusion distance is far away from a difficult deformation area and enters an easy deformation area, the coordination deformation of the intermetallic elements is facilitated, and the dendritic crystal in the cast structure can be crushed by adopting the larger reduction rate for the first time, the newly generated combination interface at the combination part is increased, the inclusion at the combination part is reduced and is crushed and separated, and the invention is prepared for the. Because the ductility of the steel plate is different from that of the copper alloy, the copper alloy is inevitably spread to the periphery by rolling, and the copper alloy is inevitably spread to the periphery and simultaneously generates extrusion force and transverse tearing force, so that the surface and the bonding interface of the copper alloy are prevented from cracking, the bonding part of the interface and a matrix tissue are uniform and fine, the subsequent small-deformation multi-pass rolling production is adopted, the copper alloy is arranged at the upper part in the rolling process, and the steel plate is arranged at the lower part, so that the abrasion and the scratch of the copper alloy are prevented. In the invention, the total reduction rate in the rolling process is controlled to be 50-60%, on one hand, the distribution of brittle inclusions and oxides at the interface is more dispersed, and the metallurgical bonding is formed at the composite interface; on one hand, the crystal grains slide, dislocation entanglement occurs, the crystal grains are elongated, broken and fiberized, and the resistance to plastic deformation of the metal is increased, so that the shearing strength and the tensile strength are further improved. If the deformation rate is further increased, the thickness of the bonding interface diffusion layer is hardly influenced, namely, the bonding interface performance is hardly changed, and incompatible deformation is easily generated in the rolling process due to the mechanical property difference of the copper alloy and the steel, so that the composite material is easily influenced by further increasing the deformation rate. Preferably, the hot rolling process is under inert gas or vacuum protection.
(6) And (3) heat treatment: then carrying out tempering heat treatment on the hot-rolled composite plate; tempering temperature is 500-550 ℃, net heat preservation time is 2-3 h, and discharging from the furnace and air cooling to room temperature. Because the diffusion degree of metal atoms in the composite material bonding layer is limited, and certain internal stress exists in the rolling process, the strength of the composite material is reduced. Therefore, the tempering heat treatment is adopted to diffuse the elements, which is beneficial to improving the strength of the bonding interface, reducing the internal stress among atoms of the composite interface, further improving the diffusion efficiency of the atoms, and simultaneously effectively removing the stress residue caused by rolling, thereby ensuring that the product has good comprehensive mechanical property and good metallurgical bonding. Preferably, the heat treatment process is under inert gas protection or vacuum protection.
Further, any process in the step (2), the step (4) and the step (6) adopts inert gas or vacuum protection; the inert gas is argon; the purpose is to prevent oxidation of the copper alloy.
The invention has the beneficial effects that:
the bimetal composite material is formed by compounding a copper alloy plate and a base plate steel plate. The copper alloy plate adopts the design idea of increasing Sn and reducing Ni, and the joint action of Si and Mn to improve the strength of the copper alloy, so that the mechanical property and the elastic property of the copper alloy can be improved, and the manufacturing cost is reduced. The copper-steel bimetal composite material is obtained by matching with the production processes of pretreatment, preheating, solid-liquid compounding, composite plate blank heating, hot rolling, straightening and heat treatment of a matrix copper alloy steel plate, so that the material has the cross-section Vickers hardness of 192-208 HV, the cross-section hardness difference is less than or equal to 16HV, the Z-direction tensile strength Rm is more than or equal to 440MPa, the elongation A is more than or equal to 25%, the composite interface shear strength is 240-260 MPa, the bending test is qualified, and meanwhile, the copper-steel bimetal composite material has good seawater corrosion resistance. The bimetal composite material has wide application prospect in ocean engineering.
Detailed Description
The present invention is further illustrated by the following examples.
The embodiment of the invention adopts the technical scheme that the specific process comprises the steps of steel plate pretreatment, preheating, solid-liquid compounding, composite plate blank heating, hot rolling, straightening and heat treatment.
(1) Pretreatment of a steel plate: firstly, milling a groove on the surface of a steel plate, wherein the depth of the groove is 5-8 mm, mechanically polishing, pickling, washing and drying the surface of the groove to polish rust on the surface of the groove to expose a bright fresh metal surface, then degreasing the steel plate, heating degreasing liquid to 60-70 ℃ to degrease the surface of the steel plate, and drying the steel plate for later use after coating an antioxidant;
(2) preheating: heating the pretreated steel plate to 850-900 ℃, and placing the steel plate in a mold cavity;
(3) solid-liquid compounding: filling a die cavity with inert gas before casting, then rapidly casting the smelted copper alloy molten metal on the surface of the pretreated steel plate, wherein the casting temperature is 1150-1200 ℃, then air-cooling, and air-cooling until the side temperature of the copper alloy is 950-980 ℃; taking out the cast blank, immediately spraying cooling water on the bottom of the steel plate for cooling until the cast blank is cooled to 200-250 ℃, immediately coating an antioxidant on the copper alloy side, then air-cooling to room temperature, and performing subsequent machining to obtain a copper-steel bimetal composite plate blank;
(4) heating the composite plate blank: heating the composite plate blank at 910-960 ℃, and preserving heat for 2-3 h in a soaking section;
(5) hot rolling: the rolling temperature is controlled to be 800-850 ℃, the first pass rolling reduction is controlled to be 15% -17%, and the total rolling reduction is 50% -60%;
(6) and (3) heat treatment: and then carrying out tempering heat treatment on the hot-rolled composite plate, wherein the tempering temperature is 500-550 ℃, the net heat preservation time is 2-3 h, and discharging from the furnace and air cooling to room temperature.
The thickness of the copper alloy plate blank in the bimetal composite plate blank in the step (3) is 5-8 mm, and the ratio of the thickness of the copper alloy plate blank to the thickness of the steel plate blank is 1: (5-10).
And (3) the die cavity in the step (2) is a graphite die cavity.
Any one of the processes from the step (2), the step (4) to the step (6) can adopt inert gas or vacuum protection. The inert gas is argon.
The composition of the composite material of the examples of the present invention is shown in Table 1. The main process parameters of the composite material pretreatment and the casting of the embodiment of the invention are shown in the table 2. The main process parameters of the composite material heating and hot rolling of the embodiment of the invention are shown in Table 3. The heat treatment process of the composite material of the embodiment of the invention is shown in Table 4. The vickers hardness of the composite materials of the examples of the present invention are shown in table 5. The Z-direction tensile properties of the composites of the examples of the invention are shown in Table 6. The shear strength and bending property of the composite interface of the composite material of the embodiment of the invention are shown in Table 7. The average corrosion rate and the maximum pitting depth of the composite material of the embodiment of the invention are shown in Table 8.
TABLE 1 composition of composites of inventive examples (wt%)
TABLE 2 main process parameters of composite material pretreatment and casting in the examples of the present invention
TABLE 3 examples of the invention the main process parameters for heating and hot rolling of composites
Table 4 composite material heat treatment process of the present invention
| Examples | Heating temperature/. degree.C | Holding time/h |
| 1 | 510 | 2.5 |
| 2 | 550 | 2.3 |
| 3 | 525 | 2.9 |
| 4 | 518 | 3.0 |
| 5 | 500 | 2.1 |
| 6 | 505 | 2.0 |
| 7 | 520 | 2.4 |
| 8 | 530 | 2.7 |
| 9 | 540 | 2.8 |
| 10 | 545 | 2.2 |
TABLE 5 Vickers hardness of composites of examples of the invention
TABLE 6Z-direction tensile Properties of composites of examples of the invention
| Examples | Rm(MPa) | A(％) |
| 1 | 445 | 25.6 |
| 2 | 448 | 25.2 |
| 3 | 442 | 25.9 |
| 4 | 440 | 26.2 |
| 5 | 449 | 25.0 |
| 6 | 450 | 25.0 |
| 7 | 441 | 26.3 |
| 8 | 447 | 25.7 |
| 9 | 444 | 25.8 |
| 10 | 443 | 26.1 |
TABLE 7 composite interface shear strength and bending Properties of the composites of the examples of the invention
TABLE 8 average corrosion rate and maximum pitting depth for composites of examples of the invention
| Examples | Average Corrosion Rate (mm/a) | Maximum pitting depth (mm) |
| 1 | 0.015 | 0.078 |
| 2 | 0.0137 | 0.077 |
| 3 | 0.0146 | 0.071 |
| 4 | 0.014 | 0.072 |
| 5 | 0.012 | 0.075 |
| 6 | 0.0135 | 0.079 |
| 7 | 0.013 | 0.074 |
| 8 | 0.0127 | 0.073 |
| 9 | 0.0138 | 0.076 |
| 10 | 0.0126 | 0.070 |
Remarking: and (3) corrosion test: the copper side (specification 50X 20X 2mm) of each example was tested for an average corrosion rate and maximum pitting depth of 3 months at an artificial seawater (pH 8) temperature of 25 deg.C
In order to express the present invention, the above embodiments are properly and fully described by way of examples, and the above embodiments are only used for illustrating the present invention and not for limiting the present invention, and those skilled in the relevant art can make various changes and modifications without departing from the spirit and scope of the present invention, and any modifications, equivalent substitutions, improvements, etc. made by the persons skilled in the relevant art should be included in the protection scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (9)
1. The copper-steel solid-liquid composite bimetallic material for ocean engineering is characterized in that a base plate in the bimetallic composite material is a steel plate, and a copper alloy plate is attached to the surface of the steel plate; the copper alloy comprises the following components in percentage by weight: ni: 15.0% -25.0%, Zn: 5.0% -10.0%, Sn: 0.5% -1.0%, Si: 2.0% -3.0%, Mn: 0.5% -1.3%, Fe: 1.0-1.5 percent, and the balance of Cu and inevitable impurities; the steel comprises the following components in percentage by weight: c: 0.07 to 0.15%, Si: 0.15-0.25%, Mn: 1.30-1.40%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, Cr: 0.10% -0.20%, V: 0.05-0.10%, Mo: 0.02% -0.08%, B: 0.002% -0.003%, and the balance of Fe and inevitable impurities.
2. The copper-steel solid-liquid composite bimetallic material for ocean engineering according to claim 1, is characterized in that the ratio of the thicknesses of the copper alloy and the steel slab is 1: (5.6-11.2).
3. The copper-steel solid-liquid composite bimetal material for ocean engineering according to claim 1, wherein the copper alloy plate is attached to one surface or two surfaces of the steel plate.
4. The copper-steel solid-liquid composite bimetallic material for ocean engineering according to claim 1, wherein the composite material has a section hardness of 192-208 HV, a section hardness difference of less than or equal to 16HV, a Z-direction tensile strength Rm of more than or equal to 440MPa, an elongation A of more than or equal to 25%, and a composite interface shear strength of 240-260 MP.
5. A method for preparing the copper-steel solid-liquid composite bimetallic material for ocean engineering of claims 1-4, the concrete process comprises steel plate pretreatment, preheating, solid-liquid compounding, composite plate blank heating, hot rolling, straightening and heat treatment; the method is characterized in that:
(1) pretreatment of a steel plate: firstly, milling a groove on the surface of a steel plate, wherein the depth of the groove is 5-8 mm, mechanically polishing, pickling, washing and drying the surface of the groove to polish rust on the surface of the groove to expose a bright fresh metal surface, then degreasing the steel plate, heating degreasing liquid to 60-70 ℃ to degrease the surface of the steel plate, and drying the steel plate for later use after coating an antioxidant;
(2) preheating: heating the pretreated steel plate to 850-900 ℃, and placing the steel plate in a mold cavity;
(3) solid-liquid compounding: filling a die cavity with inert gas before casting, then rapidly casting the smelted copper alloy molten metal on the surface of the pretreated steel plate, wherein the casting temperature is 1150-1200 ℃, then air-cooling, and air-cooling until the side temperature of the copper alloy is 950-980 ℃; taking out the cast blank, immediately spraying cooling water on the bottom of the steel plate for cooling until the cast blank is cooled to 200-250 ℃, then air-cooling to room temperature, and performing subsequent machining to obtain a copper-steel bimetal composite plate blank;
(4) heating the composite plate blank: heating the composite plate blank at 910-960 ℃, and preserving heat for 2-3 h in a soaking section;
(5) hot rolling: the rolling temperature is controlled to be 800-850 ℃, the first pass rolling reduction is controlled to be 15% -17%, and the total rolling reduction is 50% -60%;
(6) and (3) heat treatment: and then carrying out tempering heat treatment on the hot-rolled composite plate, wherein the tempering temperature is 500-550 ℃, the net heat preservation time is 2-3 h, and discharging from the furnace and air cooling to room temperature.
6. The preparation method of the copper-steel solid-liquid composite bimetal material for ocean engineering according to claim 5, wherein the thickness of the copper alloy plate blank in the bimetal composite plate blank in the step (3) is 5-8 mm, and the ratio of the thickness of the copper alloy plate blank to the thickness of the steel plate blank is 1: (5-10).
7. The preparation method of the copper-steel solid-liquid composite bimetallic material for ocean engineering according to claim 5, wherein the mold cavity in the step (2) is a graphite mold cavity.
8. The method for preparing the copper-steel solid-liquid composite bimetal material for ocean engineering according to claim 5, wherein any one of the steps (2), (4) and (6) can be protected by inert gas or vacuum.
9. The method for preparing the copper-steel solid-liquid composite bimetallic material for ocean engineering according to claim 8, wherein the inert gas is argon.
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| CN114273421A (en) * | 2021-12-22 | 2022-04-05 | 安徽工业大学 | Method for preparing carbon steel-stainless steel composite board for lining board in micro-oxidation atmosphere |
| CN114686792A (en) * | 2022-04-07 | 2022-07-01 | 刘厚新 | Continuous preparation method of bimetal material jet composite board |
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| CN105463170A (en) * | 2015-11-12 | 2016-04-06 | 内蒙古包钢钢联股份有限公司 | Production method of steel plate for 36Kg level ocean platform |
| CN108179351A (en) * | 2018-01-23 | 2018-06-19 | 东北大学 | A kind of cupric low carbon high-strength high-ductility offshore platform steel and preparation method thereof |
| CN110592473A (en) * | 2019-09-02 | 2019-12-20 | 鞍钢股份有限公司 | High-grade super-thick double-sided wear-resistant composite board and production method thereof |
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| CN105463170A (en) * | 2015-11-12 | 2016-04-06 | 内蒙古包钢钢联股份有限公司 | Production method of steel plate for 36Kg level ocean platform |
| CN108179351A (en) * | 2018-01-23 | 2018-06-19 | 东北大学 | A kind of cupric low carbon high-strength high-ductility offshore platform steel and preparation method thereof |
| CN110592473A (en) * | 2019-09-02 | 2019-12-20 | 鞍钢股份有限公司 | High-grade super-thick double-sided wear-resistant composite board and production method thereof |
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| CN114273421A (en) * | 2021-12-22 | 2022-04-05 | 安徽工业大学 | Method for preparing carbon steel-stainless steel composite board for lining board in micro-oxidation atmosphere |
| CN114273421B (en) * | 2021-12-22 | 2024-04-19 | 安徽工业大学 | Method for preparing carbon steel-stainless steel composite board for lining board in micro-oxidation atmosphere |
| CN114686792A (en) * | 2022-04-07 | 2022-07-01 | 刘厚新 | Continuous preparation method of bimetal material jet composite board |
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