WO2018099326A1 - 一种超级奥氏体不锈钢轧制复合钢板及其制造方法 - Google Patents

一种超级奥氏体不锈钢轧制复合钢板及其制造方法 Download PDF

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WO2018099326A1
WO2018099326A1 PCT/CN2017/112818 CN2017112818W WO2018099326A1 WO 2018099326 A1 WO2018099326 A1 WO 2018099326A1 CN 2017112818 W CN2017112818 W CN 2017112818W WO 2018099326 A1 WO2018099326 A1 WO 2018099326A1
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stainless steel
austenitic stainless
composite
super austenitic
layer
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English (en)
French (fr)
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张爱文
梁晓军
焦四海
丁建华
王治宇
郝英敏
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宝山钢铁股份有限公司
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Priority to EP17875616.9A priority Critical patent/EP3549760A4/en
Priority to JP2019527295A priority patent/JP6857729B2/ja
Publication of WO2018099326A1 publication Critical patent/WO2018099326A1/zh

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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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
    • 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
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
    • B32B37/085—Quenching
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/144—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers using layers with different mechanical or chemical conditions or properties, e.g. layers with different thermal shrinkage, layers under tension during bonding
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

Definitions

  • the invention relates to a composite steel plate and a manufacturing method thereof, in particular to a composite steel plate formed by rolling composite and a manufacturing method thereof.
  • composite steel plate As an important steel material, composite steel plate has unique comprehensive performance advantages of stainless steel corrosion resistance and mechanical properties of carbon steel, making it widely used in seawater desalination, heat exchangers, paper making equipment, phosphoric acid storage tanks, and smoke. Gas desulfurization equipment, power station condensation pipes, military and shipbuilding industries. With the rapid development of China's industry and the increasing service life requirements of various military and civilian equipment, as well as the requirements for green and ultra-low carbon emissions during production and use, the performance requirements for composite panels have also increased.
  • the composite steel sheet is usually subjected to conventional mechanical compounding and explosive composite, and the above two processes can be separately controlled while controlling the composite layer and the performance of the base layer, and then combined. That is, before the compounding, the respective required properties of the stainless steel and the carbon steel can be respectively processed to a suitable state, and then the mechanical composite force or the explosive impact force is applied to combine them into one to obtain a composite plate.
  • these two composite methods each have their own shortcomings. For example, a mechanical composite composite panel has no complete metallurgical bond between the stainless steel composite layer and the carbon steel base layer, but is simply attached by mechanical force.
  • the composite interface is easy to crack and fall off during use, and the failure is fast;
  • the disadvantage of explosion composite is that
  • the process method itself has strict requirements on the process environment, and it needs to be carried out in the deep forests and old places where the environment is sparsely populated.
  • the noise, vibration and shock waves generated during the explosion have a great impact on the surrounding environment.
  • this process The method is limited by environmental factors.
  • the composite panel produced by explosive composite has a low shear strength at the composite interface.
  • One of the objects of the present invention is to provide a super austenitic stainless steel rolled composite steel sheet which is obtained by composite rolling so that the obtained super austenitic stainless steel rolled composite steel sheet has high strength, good cold bending property and corrosion resistance.
  • the present invention provides a super austenitic stainless steel rolled composite steel plate comprising a base layer and a super austenitic stainless steel composite layer rolled and laminated on the base layer; the chemical element mass percentage of the base layer is:
  • Carbon is an important alloying element in steel.
  • the increase in carbon content can increase the strength and hardness of the steel sheet, but at the same time it will also cause the plastic toughness of the steel sheet to decrease.
  • the influence of carbon on the performance of the base steel sheet is comprehensively considered, and the diffusion and migration of carbon into the super austenitic stainless steel layer during rolling compounding are considered, and thus the mass percentage of C is limited.
  • the super austenitic stainless steel used in the super austenitic stainless steel layer has a mass percentage of carbon of less than 0.03%, the mass percentage of carbon in the base layer is controlled to 0.02-0.09% to reduce the influence of carbon on the corrosion resistance of the stainless steel. At the same time, the mechanical properties and welding properties of the base layer are guaranteed. .
  • Si Silicon is added to the steel to improve the purity of the steel, and Si acts as a deoxidation.
  • silicon plays a solid solution strengthening effect in steel, but excessive silicon is disadvantageous to the welding property of steel.
  • the Si in the base layer is limited to 0 ⁇ Si ⁇ 0.35%, and the silicon in this range has a low influence on the corrosion resistance of the super austenitic stainless steel double layer, and The base layer is provided with good welding properties.
  • Mn In the technical solution described in the present invention, manganese functions to stabilize the austenite structure, at the same time contribute to increase the hardenability of the steel, and is advantageous for reducing the critical cooling rate of martensite formation.
  • the excess manganese has a higher segregation tendency, and the mass percentage of manganese in the super austenitic stainless steel layer is less than 2.0%. Therefore, the base layer of the super austenitic stainless steel rolled composite steel sheet of the present invention is Mn.
  • the mass percentage is limited to 1.0 to 2.0%.
  • the Mn in this range does not cause adverse effects on the super austenitic stainless steel double layer, and at the same time contributes to the improvement of the strength level of the steel.
  • the mass percentage of manganese is controlled to be 1.5 to 1.7%.
  • Al is a strong deoxidizing element.
  • the mass percentage of aluminum is controlled to be 0.02 to 0.04%.
  • excess aluminum in the deoxidation and nitrogen in the steel can form AlN precipitates, thereby increasing the strength of the steel and refining the austenite grain size of the steel during heat treatment.
  • Ti is a strong carbide forming element.
  • the addition of a small amount of Ti in the steel is beneficial to the fixation of N in the steel.
  • the TiN formed can make the austenite grains of the base layer not excessively grow when the composite billet is heated, and refine the original austenite. Grain size.
  • Titanium can also be combined with carbon and sulfurized in steel to form TiC, TiS, Ti 4 C 2 S 2 , and the above compounds exist in the form of inclusions and second phase particles.
  • the above carbonitride precipitates of titanium can also prevent grain growth in the heat-affected zone during soldering and improve soldering performance. Therefore, the mass percentage of Ti according to the present invention is controlled to be 0.005 to 0.018%.
  • Nb niobium is a strong carbide forming element.
  • the addition of niobium to the base layer is mainly for increasing the recrystallization temperature, so that the base layer is subjected to austenite recrystallization rolling. After the end, the crystal grains cannot grow rapidly, which is beneficial to the improvement of the low temperature impact toughness of the steel of the base layer. Therefore, the super austenite of the present invention is stainless
  • the mass percentage of Nb in the base layer of the steel rolled composite steel sheet is controlled to be 0.010 to 0.030%.
  • N is an austenite stabilizing element which is a residual margin as a steelmaking gas element in the base layer, and therefore, the mass percentage of N in the austenitic stainless steel rolled composite steel sheet according to the present invention is controlled at N ⁇ 0.006%.
  • the inevitable impurities are mainly S and P elements, and thus it is necessary to control P ⁇ 0.015% and S ⁇ 0.010% in the base layer.
  • the mass percentage of the super austenitic stainless steel double layer to S needs to be controlled to 0.01% or less.
  • the base layer further contains at least one of Ni, Cr and Mo elements, wherein Ni ⁇ 0.20%, Cr ⁇ 0.20%, Mo ⁇ 0.10 %.
  • Ni is an element that stabilizes austenite, which is beneficial to further increase the strength of steel.
  • the addition of nickel to steel can significantly increase the low temperature impact toughness of steel. Since nickel is a precious alloying element, excessive addition causes an increase in production cost. Therefore, the mass percentage of the base layer of the super austenitic stainless steel rolled composite steel sheet according to the present invention to nickel is limited to Ni ⁇ 0.20%.
  • the mass percentage of Cr in the base layer of the super austenitic stainless steel rolled composite steel sheet according to the present invention is limited to Cr ⁇ 0.20%.
  • Molybdenum can refine grains and increase the strength and toughness of steel.
  • molybdenum can reduce the temper brittleness of steel, and it can precipitate very fine carbides during tempering, which significantly strengthens the base matrix of steel.
  • the addition of molybdenum is advantageous for suppressing the self-temper brittleness generated during the air cooling process of the super austenitic stainless steel rolled composite steel sheet according to the present invention after water cooling and cooling, however, since excessive addition of molybdenum increases production cost,
  • the mass percentage of molybdenum in the base layer of the super austenitic stainless steel rolled composite steel sheet according to the present invention is limited to Mo ⁇ 0.10%.
  • the super austenitic stainless steel double layer may be a super austenitic stainless steel, such as S31254 (254SMo), S32654 (654SMo), N08904 (904L), N08367, N08926 or other technical in the field.
  • Super austenitic stainless steel known to personnel.
  • the microstructure of the super austenitic stainless steel double layer is austenite, and the ratio of the delta ferrite in the microstructure is not more than 5 The ratio of %, ⁇ phase does not exceed 2%.
  • the ratio of the ⁇ phase in the range of 0.5-1.0 mm of the super austenitic stainless steel composite layer is not more than 0.2%.
  • the microstructure of the base layer is bainite or bainite + a small amount of martensite or bainite + a small amount of M-A island.
  • the ratio of martensite is ⁇ 5%; when the microstructure of the base layer is bainite + a small amount of MA island, the ratio of MA islands ⁇ 5%.
  • a transition layer is provided at a joint of the base layer and the super austenitic stainless steel composite layer, and the thickness of the transition layer is ⁇ 100 ⁇ m.
  • the super austenitic stainless steel rolled composite steel plate according to the present invention has a base layer yield strength ⁇ 345 MPa, a tensile strength ⁇ 460 MPa, an elongation ratio ⁇ 20%, and a -20 ° C Charpy impact energy Akv ⁇ 100 J, -40 °C Charpy impact energy Akv ⁇ 47J, the shear strength of super austenitic stainless steel rolled composite steel plate ⁇ 365MPa.
  • Another object of the present invention is to provide a method for producing the above-described super austenitic stainless steel rolled composite steel sheet, which can obtain a super austenitic stainless steel rolled composite steel sheet having high strength.
  • the present invention also provides a method for manufacturing the above super austenitic stainless steel rolled composite steel plate, comprising the steps of:
  • the substrate slab and the multi-layer slab are assembled: at least two layers of stainless steel slab and at least two substrate slabs are welded into a composite slab, wherein the middle two layers are stainless steel slabs.
  • the outer side is a substrate slab, and a separating layer is disposed between the two layers of stainless steel multi-layer slabs;
  • Composite rolling firstly, the composite blank is heated at a temperature of 1140 to 1200 ° C, and then multi-pass rolling is performed in the austenite recrystallization region of the substrate slab and the multi-layer slab, and the finishing rolling temperature is not low. At 1000 ° C;
  • the temperature of starting water cooling is not lower than 940 ° C, the final cooling temperature is 430-550 ° C, and the cooling rate is 10-100 ° C / s;
  • the composite panel is hot-straightened, then air-cooled to room temperature in a single sheet state, and then cold-straightened.
  • the invention adopts super austenitic stainless steel as a pair of composite slab and substrate slab, and obtains a comprehensive heating, rolling and cooling process parameter design by combining the composite slab and the substrate slab to obtain a comprehensive heating, rolling and cooling process parameter design.
  • the surface of the slab to be composited is pre-processed on the substrate slab and the multi-layer slab to remove the oxide of the surface to be composited, thereby improving the composite effect.
  • a layer of separating agent is laid on the separation interface of the two-layer multi-layer slab for smooth separation of the two composite steel sheets after rolling.
  • the composite rolling heating temperature of the composite blank is between 1140 and 1200 ° C, in which the ⁇ phase and the carbide can be completely dissolved, and the alloy in the base layer can also be made.
  • the compound of the element is fully dissolved.
  • water cooling is required immediately after the completion of the composite rolling, and the water cooling method can be known to those skilled in the art. Ways such as DQ, ACC or DQ+ACC.
  • the cooling rate is controlled at 10 to 100 ° C / s, so that the base austenite grains are subjected to rapid cooling and subsequent phase transformation to obtain a bainite structure, and the grains are refined.
  • the water-cooled final cooling temperature is 430 to 470 °C.
  • the finishing temperature is 1020 to 1060 °C.
  • the super austenitic stainless steel rolled composite steel plate according to the invention is controlled by optimized composition design and process parameters, so that the obtained super austenitic stainless steel rolled composite steel plate has a base layer yield strength ⁇ 345 MPa and a tensile strength ⁇ 460 MPa.
  • the manufacturing method of the present invention enables the composite steel sheet to have both excellent mechanical properties and excellent corrosion resistance of super austenitic stainless steel by composite rolling of the substrate slab and the composite slab.
  • Example 1 is a photograph showing the microstructure of the base layer of the super austenitic stainless steel rolled composite steel plate of Example 2.
  • Example 2 is a photograph showing a multi-layer microstructure of a super austenitic stainless steel rolled composite steel plate of Example 2.
  • Example 3 is a photomicrograph showing the microstructure of the base layer and the interlayer transition layer of the super austenitic stainless steel rolled composite steel sheet of Example 2.
  • Table 1 lists the mass percentages of the chemical elements of the respective layers of the super austenitic stainless steel rolled composite steel sheets of Examples 1-10.
  • the manufacturing method of the super austenitic stainless steel rolled composite steel plate of Example 1-10 was prepared by the following steps (see Table 2 for specific process parameters in each example):
  • the substrate slab and the composite slab are assembled: two layers of stainless steel slab and two slab slabs are welded into a composite slab, wherein the middle two layers are stainless steel slabs, outer side a base layer slab, a separating layer is disposed between the two layers of stainless steel slabs;
  • Composite rolling firstly, the composite blank is heated at a temperature of 1140 to 1200 ° C, and then multi-pass rolling is performed in the austenite recrystallization region of the substrate slab and the multi-layer slab, and the finishing rolling temperature is not low. At 1000 ° C;
  • the temperature of starting water cooling is not lower than 940 ° C, the final cooling temperature is 430-550 ° C, and the cooling rate is 10-100 ° C / s;
  • the composite panel is hot-straightened, then air-cooled to room temperature in a single sheet state, and then cold-straightened.
  • the substrate slab forms the base layer of the super austenitic stainless steel rolled composite steel plate of each embodiment
  • the double-layer stainless steel slab forms the composite layer of the super austenitic stainless steel rolled composite steel plate of each embodiment.
  • Table 2 lists the specific process parameters of the method for producing the super austenitic stainless steel rolled composite steel sheets of Examples 1-10.
  • Table 3 lists the mechanical properties test results of the super austenitic stainless steel rolled composite steel sheets of Examples 1-10 and the layers microstructure.
  • the base layer yield strength of the super austenitic stainless steel rolled composite steel sheets of Examples 1-10 is ⁇ 345 MPa
  • the tensile strength is ⁇ 460 MPa
  • the elongation is ⁇ 20%
  • the -20 ° C Charpy impact energy Akv ⁇ 100J, -40 °C Charpy impact work Akv ⁇ 47J
  • super austenitic stainless steel rolled composite steel plate shear strength ⁇ 365MPa thus indicating that the mechanical properties of the examples are good.
  • the results of the cold bending test of the super austenitic stainless steel rolled composite steel sheets of the respective examples Qualified indicates excellent cold bending and forming properties.
  • Example 2 the super austenitic stainless steel rolled composite steel plate of Example 2 was peeled off, and the sample was subjected to 6% ferric chloride etching test.
  • the test method was in accordance with GB/T 17897-1999, and the pitting corrosion test results are listed in the table. 4.
  • Example 2-3 the super austenitic stainless steel rolled composite steel plate of Example 2-3 was peeled off, and the sample was subjected to sulfuric acid-copper sulfate corrosion test.
  • the test method was in accordance with GB/T4334-2008, and the intergranular corrosion test results are listed in Table 5. .
  • Example 1 is a photograph showing the microstructure of the base layer of the super austenitic stainless steel rolled composite steel plate of Example 2. As can be seen from Fig. 1, the base layer microstructure of Example 2 is bainite.
  • Example 2 is a photograph showing a multi-layer microstructure of a super austenitic stainless steel rolled composite steel plate of Example 2. As can be seen from Fig. 2, the multi-layer microstructure of Example 2 is austenite.
  • Example 3 is a photomicrograph showing the microstructure of the base layer and the interlayer transition layer of the super austenitic stainless steel rolled composite steel sheet of Example 2. As can be seen from FIG. 3, the transition layer is located at the junction of the base layer and the composite layer, and the thickness of the transition layer is ⁇ 100 ⁇ m.

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  • Organic Chemistry (AREA)
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Abstract

一种超级奥氏体不锈钢轧制复合钢板及其制造方法，包括基层和轧制复合于基层上的超级奥氏体不锈钢复层；所述基层的化学元素质量百分比为：C：0.02～0.09％、0＜Si≤0.35％、Mn：1.0～2.0％、Al：0.02～0.04％、Ti：0.005～0.018％、Nb：0.010～0.030％、N≤0.006％，余量为铁和其他不可避免杂质；采用焊接后轧制复合，复合钢板的剪切强度≥365MPa。

Description

一种超级奥氏体不锈钢轧制复合钢板及其制造方法 技术领域
本发明涉及一种复合钢板及其制造方法，尤其涉及一种采用轧制复合形成的复合钢板及其制造方法。
背景技术
复合钢板作为一种重要的钢铁材料，其独特的兼具不锈钢耐蚀性能和碳钢力学性能的综合性能优势，使之被广泛应用于海水淡化、热交换器、造纸设备、磷酸储罐、烟气脱硫装置、电站冷凝管、军工及船舶制造等行业。随着我国工业的飞速发展以及各类军用及民用设备的使用寿命的要求提升，以及生产及使用过程的对绿色环保超低碳排放的要求，使得对复合板的性能要求也随之提高。
现有技术中，复合钢板通常采用传统的机械复合和爆炸复合，上述两种工艺在控制复合板复层和基层性能的时候能够分开控制，然后再将其组合在一起。即在复合前可以分别将不锈钢和碳钢的各自所要求的性能处理到合适的状态，再施以机械复合力或爆炸冲击力使之合二为一，获得复合板。但是这两种复合方法各有各的缺点。例如：机械复合的复合板其不锈钢复层和碳钢基层中间没有完整的冶金结合，只是通过机械的力贴在一起，使用过程中复合界面容易开裂、脱落，失效快；爆炸复合的缺点是其本身工艺方法对工艺环境要求较为严格，需要在深山老林，环境人烟稀少的地方执行，此外，爆炸时产生的噪音、震动和冲击波对周边环境影响极大，在环境意识崛起的当前时期，这种工艺方法受环境条件因素限制较大。另外，爆炸复合生产的复合板其复合界面的剪切强度较低。
发明内容
本发明的目的之一在于提供一种超级奥氏体不锈钢轧制复合钢板，通过复合轧制使得所获得的超级奥氏体不锈钢轧制复合钢板的强度高，冷弯性能良好且耐腐蚀。
为了实现上述目的，本发明提出了一种超级奥氏体不锈钢轧制复合钢板，包括基层和轧制复合于基层上的超级奥氏体不锈钢复层；所述基层的化学元素质量百分比为：
C：0.02～0.09％、0＜Si≤0.35％、Mn：1.0～2.0％、Al：0.02～0.04％、Ti：0.005～0.018％、Nb：0.010～0.030％、N≤0.006％，余量为铁和其他不可避免杂质。
其中，本发明所述的超级奥氏体不锈钢轧制复合钢板的基层的各化学元素的设计原理如下所述：
C：碳是钢中重要的合金元素。碳含量的提高能使钢板的强度和硬度得到提升，但同时也会导致钢板的塑性韧性下降。在本发明所述的技术方案中，综合考虑碳对基层钢板性能的影响，同时考虑到轧制复合时碳向超级奥氏体不锈钢复层的扩散迁移，因而，对C的质量百分比进行了限定。由于超级奥氏体不锈钢复层所采用的超级奥氏体不锈钢的碳的质量百分比低于0.03％，因而基层的碳的质量百分比控制在0.02-0.09％，以减少碳对不锈钢耐蚀性的影响，同时保证基层的力学性能和焊接性能。。
Si：钢中加硅用以提高钢的纯净度，并且Si起到脱氧的作用。在本发明技术方案中，硅在钢中起固溶强化作用，但过量的硅不利于钢的焊接性能。鉴于超级奥氏体不锈钢复层中也具有硅，因而，对基层中Si限定在0＜Si≤0.35％，在此范围内的硅对超级奥氏体不锈钢复层的耐蚀性影响低，并且使得基层具有良好的焊接性能。
Mn：在本发明所述的技术方案中，锰起到稳定奥氏体组织的作用，同时有助于增加钢的淬透性，并且有利于降低马氏体形成的临界冷速。然而过量的锰具有较高的偏析倾向，同时超级奥氏体不锈钢复层中锰的质量百分比低于2.0％，因此，本发明所述的超级奥氏体不锈钢轧制复合钢板的基层对Mn的质量百分比限定在1.0～2.0％。在此范围内的Mn既不造成对超级奥氏体不锈钢复层的不良影响，同时有利于提高钢的强度级别。
考虑到锰与碳的互相作用，为了进一步提高本发明所述的超级奥氏体不锈钢轧制复合钢板的强度，在一些优选的实施方式中，锰的质量百分比控制在1.5-1.7％。
Al：在本发明所述的技术方案中，Al是强脱氧元素。为了降低钢中的氧元素的含量，铝的质量百分比控制在0.02～0.04％。此外，脱氧后多余的铝和钢中的氮元素能形成AlN析出物，从而提高钢的强度并且在热处理加热时能细化钢的奥氏体晶粒度。
Ti：Ti是强碳化物形成元素，钢中加入微量的Ti有利于固定钢中的N，形成的TiN能使复合坯加热时基层奥氏体晶粒不过分长大，细化原始奥氏体晶粒度。钛在钢中还可分别与碳和硫化合生成TiC、TiS、Ti4C2S2，上述化合物以夹杂物和第二相粒子的形式存在。钛的上述碳氮化物析出物在焊接时还可阻止热影响区晶粒长大，改善焊接性能。因此，本发明所述的Ti的质量百分比控制在0.005-0.018％。
Nb：铌是强碳化物形成元素，在本发明所述的超级奥氏体不锈钢轧制复合钢板中，在基层中加入铌主要是为了提高再结晶温度，使得基层在奥氏体再结晶轧制结束后晶粒不能迅速长大，有利于基层的钢的低温冲击韧性的提高。因此，本发明所述的超级奥氏体不锈 钢轧制复合钢板的基层中对Nb的质量百分比控制在0.010～0.030％。
N：N是奥氏体稳定化元素，其在基层中是作为炼钢气体元素的残留余量，因而，在本发明所述的奥氏体不锈钢轧制复合钢板中对N的质量百分比控制在N≤0.006％。
在本发明所述的超级奥氏体不锈钢轧制复合钢板中，不可避免的杂质主要是S和P元素，因而需要控制基层中P≤0.015％，S≤0.010％。
需要说明的是，作为影响钢冲击韧性的主要杂质元素，超级奥氏体不锈钢复层对于S的质量百分比也需要控制在0.01％以下。
进一步地，本发明所述的超级奥氏体不锈钢轧制复合钢板中，所述基层还含有Ni、Cr和Mo元素的至少其中之一，其中Ni≤0.20％、Cr≤0.20％、Mo≤0.10％。
为了进一步提高本发明所述的奥氏体不锈钢轧制复合钢板的实施效果，上述化学元素的设计原理如下所述：
Ni：Ni是稳定奥氏体的元素，有利于进一步提高钢的强度。此外，钢中添加镍能大幅提高钢的低温冲击韧性。由于镍属于贵重合金元素，添加过多会造成生产成本的提高。因而，本发明所述的超级奥氏体不锈钢轧制复合钢板的基层对镍的质量百分比限定在Ni≤0.20％。
Cr：由于铬的偏析倾相较锰小，因而，当基层的钢中有明显的偏析带及带状组织的时候，通过添加铬来改善钢的性能。此外，基层中添加铬也有利于抑制超级奥氏体不锈钢复层中的铬向基层的扩散。鉴于此，本发明所述的超级奥氏体不锈钢轧制复合钢板基层对Cr的质量百分比限定在Cr≤0.20％。
Mo：钼可以细化晶粒，提高钢的强度和韧性。此外，钼能减少钢的回火脆性，回火时能析出非常细小的碳化物，显著强化钢的基层基体。另外，钼的添加有利于抑制本发明所述的超级奥氏体不锈钢轧制复合钢板水冷停冷之后的空冷过程中产生的自回火脆性，然而由于过多添加钼会增加生产成本，因此，本发明所述的超级奥氏体不锈钢轧制复合钢板基层中钼的质量百分比限定在Mo≤0.10％。
在本发明所述的技术方案中，超级奥氏体不锈钢复层可采用超级奥氏体不锈钢，例如S31254(254SMo)、S32654(654SMo)、N08904(904L)、N08367、N08926或其他本领域内技术人员知晓的超级奥氏体不锈钢。
优选地，本发明所述的超级奥氏体不锈钢轧制复合钢板中，所述超级奥氏体不锈钢复层的微观组织主体为奥氏体，微观组织中δ铁素体的相比例不超过5％，σ相的相比例不超过2％。
更进一步优选地，本发明所述的超级奥氏体不锈钢轧制复合钢板中，所述超级奥氏体不锈钢复层距表面0.5-1.0mm范围内的σ相的相比例不超过0.2％。
进一步地，本发明所述的超级奥氏体不锈钢轧制复合钢板中，所述基层的微观组织为贝氏体或贝氏体+少量马氏体或贝氏体+少量M-A岛。
更进一步地，当基层的微观组织为贝氏体+少量马氏体时，马氏体的相比例≤5％；当基层的微观组织为贝氏体+少量M-A岛时，M-A岛的相比例≤5％。
进一步地，本发明所述的超级奥氏体不锈钢轧制复合钢板中，在基层和超级奥氏体不锈钢复层的结合处具有过渡层，所述过渡层的厚度≤100μm。
进一步地，本发明所述的超级奥氏体不锈钢轧制复合钢板，其基层屈服强度≥345MPa，抗拉强度≥460MPa，延伸率≥20％，-20℃夏比冲击功Akv≥100J，-40℃夏比冲击功Akv≥47J，超级奥氏体不锈钢轧制复合钢板的剪切强度≥365MPa。
本发明的另一目的还在于提供一种可用于制造上述超级奥氏体不锈钢轧制复合钢板的制造方法，采用该制造方法可以获得强度高的超级奥氏体不锈钢轧制复合钢板。
为了达到上述发明目的，本发明还提出了一种上述的超级奥氏体不锈钢轧制复合钢板的制造方法，包括步骤：
(1)制得基板板坯和复层不锈钢板坯；
(2)将基板板坯和复层板坯进行组坯：将至少两层不锈钢复层板坯和至少两层基板板坯组坯焊接成复合坯，其中中间两层为不锈钢复层板坯，外侧为基板板坯，两层不锈钢复层板坯之间铺设分离剂层；
(3)复合轧制：先将复合坯在1140～1200℃的温度下加热，然后在基板板坯和复层板坯的奥氏体再结晶区进行多道次轧制，终轧温度不低于1000℃；
(4)完成复合轧制后立即水冷，开始水冷的温度不低于940℃，终冷温度为430-550℃，冷却速度为10-100℃/s；
(5)复合板热矫直，然后在单张状态下空冷至室温，然后冷矫直。
本发明采用超级奥氏体不锈钢作为复层板坯和基板板坯配对，通过将复层板坯与基板板坯复合形成的复合坯施以合理的加热、轧制和冷却工艺参数设计，获得综合性能优良的超级奥氏体不锈钢轧制复合钢板。
在基板板坯和复层板坯组坯前，对基板板坯与复层板坯需要复合的板坯表面进行预处理，去除需要复合的表面的氧化物，从而提高复合效果。此外，在两层复层板坯分离界面铺设一层分离剂层，用于轧后使两张复合钢板顺利分离。
为了使得复层获得均匀的奥氏体化组织，复合坯的复合轧制加热温度在1140～1200℃，在此温度范围内可以使得σ相及碳化物完全溶解，同时也能够使基层中的合金元素的化合物充分溶解。
为了使得复层中的奥氏体再结晶晶粒能够保留下来，使之不析出σ相或碳化物，因而完成复合轧制后需要立即进行水冷，水冷冷却方式可采用本领域内技术人员知晓的方式，例如DQ、ACC或DQ+ACC。冷却速率控制在10-100℃/s，从而使得基层奥氏体晶粒经快速冷却及随后的相变过程中获得贝氏体组织，晶粒得以细化。
进一步地，在本发明所述的制造方法中，在所述步骤(4)中，水冷的终冷温度为430-470℃。
进一步地，在本发明所述的制造方法中，在所述步骤(3)中，终轧温度为1020～1060℃。
本发明所述的超级奥氏体不锈钢轧制复合钢板通过优化成分设计和工艺参数控制，使得所获的超级奥氏体不锈钢轧制复合钢板其基层屈服强度≥345MPa，抗拉强度≥460MPa，延伸率≥20％，-20℃夏比冲击功Akv≥100J，-40℃夏比冲击功Akv≥47J，超级奥氏体不锈钢轧制复合钢板的剪切强度≥365MPa。
此外，本发明所述的制造方法通过将基板板坯与复层板坯的复合轧制，使得复合钢板既具有优良的力学性能，又具有超级奥氏体不锈钢的极佳耐蚀性。
附图说明
图1为实施例2的超级奥氏体不锈钢轧制复合钢板基层微观组织照片。
图2为实施例2的超级奥氏体不锈钢轧制复合钢板复层微观组织照片。
图3为实施例2的超级奥氏体不锈钢轧制复合钢板基层与复层间过渡层的微观组织照片。
具体实施方式
下面将结合说明书附图和具体的实施例对本发明所述的超级奥氏体不锈钢轧制复合钢板及其制造方法做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。
实施例1-10
表1列出了实施例1-10的超级奥氏体不锈钢轧制复合钢板各坯层的化学元素的质量百分比。
表1.(wt％，余量为Fe和除了P、S以外其他不可避免的杂质)
Figure PCTCN2017112818-appb-000001
实施例1-10的超级奥氏体不锈钢轧制复合钢板的制造方法采用以下步骤制得(各实施例中的具体工艺参数参见表2)：
(1)制得基板板坯和复层不锈钢板坯；
(2)将基板板坯和复层板坯进行组坯：将两层不锈钢复层板坯和两层基板板坯组坯焊接成复合坯，其中，中间两层为不锈钢复层板坯，外侧为基层板坯，两层不锈钢复层板坯之间铺设分离剂层；
(3)复合轧制：先将复合坯在1140～1200℃的温度下加热，然后在基板板坯和复层板坯的奥氏体再结晶区进行多道次轧制，终轧温度不低于1000℃；
(4)完成复合轧制后立即水冷，开始水冷的温度不低于940℃，终冷温度为430-550℃，冷却速度为10-100℃/s；
(5)复合板热矫直，然后在单张状态下空冷至室温，然后冷矫直。
需要说明的是，最终，基板板坯形成各实施例的超级奥氏体不锈钢轧制复合钢板的基层，复层不锈钢板坯则形成各实施例的超级奥氏体不锈钢轧制复合钢板的复层。
表2列出了实施例1-10的超级奥氏体不锈钢轧制复合钢板的制造方法的具体工艺参数。
表2.
Figure PCTCN2017112818-appb-000002
表3列出了实施例1-10的超级奥氏体不锈钢轧制复合钢板力学性能测试结果及各层的 微观组织。
表3.
Figure PCTCN2017112818-appb-000003
由表3可以看出，实施例1-10的超级奥氏体不锈钢轧制复合钢板的基层屈服强度≥345MPa，抗拉强度≥460MPa，延伸率≥20％，-20℃夏比冲击功Akv≥100J，-40℃夏比冲击功Akv≥47J，超级奥氏体不锈钢轧制复合钢板的剪切强度≥365MPa，由此说明各实施例的力学性能良好。此外，各实施例的超级奥氏体不锈钢轧制复合钢板在冷弯测试的结果 合格说明其冷弯及成型性能优良。
此外，对实施例2的超级奥氏体不锈钢轧制复合钢板剥离其复层，取样进行6％三氯化铁浸蚀测试，测试方法按照GB/T 17897-1999，点腐蚀测试结果列于表4。
表4.
Figure PCTCN2017112818-appb-000004
另外，对实施例2-3的超级奥氏体不锈钢轧制复合钢板剥离其复层，取样进行硫酸-硫酸铜腐蚀测试，测试方法按照GB/T4334-2008，晶间腐蚀测试结果列于表5。
表5.
实施例 是否有裂纹
2 无
3 无
由表4和表5可以看出，所测试的实施例的超级奥氏体不锈钢轧制复合钢板在复合后其复层的耐腐蚀性能良好。
图1为实施例2的超级奥氏体不锈钢轧制复合钢板基层微观组织照片。由图1可知，实施例2的基层微观组织为贝氏体。
图2为实施例2的超级奥氏体不锈钢轧制复合钢板复层微观组织照片。由图2可知，实施例2的复层微观组织为奥氏体。
图3为实施例2的超级奥氏体不锈钢轧制复合钢板基层与复层间过渡层的微观组织照片。由图3可知，过渡层位于基层与复层的结合处，过渡层的厚度≤100μm。
需要注意的是，以上列举的仅为本发明的具体实施例，显然本发明不限于以上实施例，随之有着许多的类似变化。本领域的技术人员如果从本发明公开的内容直接导出或联想到的所有变形，均应属于本发明的保护范围。

Claims (11)

  1. 一种超级奥氏体不锈钢轧制复合钢板，其特征在于，包括基层和轧制复合于基层上的超级奥氏体不锈钢复层；所述基层的化学元素质量百分比为：
    C：0.02～0.09％、0＜Si≤0.35％、Mn：1.0～2.0％、Al：0.02～0.04％、Ti：0.005～0.018％、Nb：0.010～0.030％、N≤0.006％，余量为铁和其他不可避免杂质。
  2. 如权利要求1所述的超级奥氏体不锈钢轧制复合钢板，其特征在于，所述基层还含有Ni、Cr和Mo元素的至少其中之一，其中Ni≤0.20％、Cr≤0.20％、Mo≤0.10％。
  3. 如权利要求1所述的超级奥氏体不锈钢轧制复合钢板，其特征在于，所述超级奥氏体不锈钢复层的微观组织主体为奥氏体，微观组织中δ铁素体的相比例不超过5％，σ相的相比例不超过2％。
  4. 如权利要求3所述的超级奥氏体不锈钢轧制复合钢板，其特征在于，所述超级奥氏体不锈钢复层距表面0.5-1.0mm范围内的σ相的相比例不超过0.2％。
  5. 如权利要求1所述的超级奥氏体不锈钢轧制复合钢板，其特征在于，所述基层的微观组织为贝氏体或贝氏体+少量马氏体或贝氏体+少量M-A岛。
  6. 如权利要求5所述的超级奥氏体不锈钢轧制复合钢板，其特征在于，当基层的微观组织为贝氏体+少量马氏体时，马氏体的相比例≤5％；当基层的微观组织为贝氏体+少量M-A岛时，M-A岛的相比例≤5％。
  7. 如权利要求1所述的超级奥氏体不锈钢轧制复合钢板，其特征在于，在基层和超级奥氏体不锈钢复层的结合处具有过渡层，所述过渡层的厚度≤100μm。
  8. 如权利要求1-7中任意一项所述的超级奥氏体不锈钢轧制复合钢板，其基层屈服强度≥345MPa，抗拉强度≥460MPa，延伸率≥20％，-20℃夏比冲击功Akv≥100J，-40℃夏比冲击功Akv≥47J，超级奥氏体不锈钢轧制复合板的剪切强度≥365MPa。
  9. 如权利要求1-8中任意一项所述的超级奥氏体不锈钢轧制复合钢板的制造方法，其特征在于，包括步骤：
    (1)制得基板板坯和复层不锈钢板坯；
    (2)将基板板坯和复层板坯进行组坯：将至少两层不锈钢复层板坯和至少两层基板板坯组坯焊接成复合坯，其中中间两层为不锈钢复层板坯，外侧为基板板坯，两层不锈钢复层板坯之间铺设分离剂层；
    (3)复合轧制：先将复合坯在1140～1200℃的温度下加热，然后在基板板坯和复层板坯的奥氏体再结晶区进行多道次轧制，终轧温度不低于1000℃；
    (4)完成复合轧制后立即水冷，开始水冷的温度不低于940℃，终冷温度为430-550℃，冷却速度为10-100℃/s；
    (5)复合板热矫直，然后在单张状态下空冷至室温，然后冷矫直。
  10. 如权利要求9所述的制造方法，其特征在于，在所述步骤(4)中，水冷的终冷温度为430-470℃。
  11. 如权利要求9所述的制造方法，其特征在于，在所述步骤(3)中，终轧温度为1020～1060℃。
PCT/CN2017/112818 2016-11-30 2017-11-24 一种超级奥氏体不锈钢轧制复合钢板及其制造方法 WO2018099326A1 (zh)

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EP3862456A4 (en) * 2018-10-01 2022-08-03 NIPPON STEEL Stainless Steel Corporation CLAD AUSTENITIC STAINLESS STEEL SHEET, BASIC STEEL SHEET AND METHOD OF PRODUCTION OF CLAD STEEL SHEET
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