CN111636013A - Novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for power station and manufacturing method - Google Patents

Novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for power station and manufacturing method Download PDF

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CN111636013A
CN111636013A CN202010534158.2A CN202010534158A CN111636013A CN 111636013 A CN111636013 A CN 111636013A CN 202010534158 A CN202010534158 A CN 202010534158A CN 111636013 A CN111636013 A CN 111636013A
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equal
cold rolling
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heat treatment
alloy
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高佩
汤云飞
赵佳敏
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JIANGSU YINHUAN PRECISION STEEL PIPE CO Ltd
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JIANGSU YINHUAN PRECISION STEEL PIPE CO Ltd
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Publication of CN111636013A publication Critical patent/CN111636013A/en
Priority to PCT/CN2020/119946 priority patent/WO2021248755A1/en
Priority to KR1020217006586A priority patent/KR20210154959A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • 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
    • B21B1/02—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 heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/02—Making uncoated products
    • B21C23/04—Making uncoated products by direct extrusion
    • B21C23/08—Making wire, bars, tubes
    • B21C23/085—Making tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D19/00—Flanging or other edge treatment, e.g. of tubes
    • B21D19/005—Edge deburring or smoothing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
    • B21J5/06—Methods for forging, hammering, or pressing; Special equipment or accessories therefor for performing particular operations
    • B21J5/12—Forming profiles on internal or external surfaces
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/021—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular fabrication or treatment of ingot or slab
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • 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
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions

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Abstract

The invention discloses a novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for a power station, which comprises the following components in percentage by weight: c: 0.03-0.10%, Si is less than or equal to 1.0%, Mn is less than or equal to 0.70%, P is less than or equal to 0.012%, S is less than or equal to 0.008%, Cr: 20.00-24.00%, Co: 10.00-15.00%, Al: 0.70-1.50%, Ti: 0.20-0.70%, Mo: 8.00-10.00%, Fe is less than or equal to 2.00%, Cu is less than or equal to 0.5%, B: 0.001-0.006 percent of the total weight of the components, less than or equal to 0.005 percent of Pb, less than or equal to 0.005 percent of Sb, less than or equal to 0.001 percent of Bi, less than or equal to 0.010 percent of Sn, less than or equal to 0.010 percent of As, and the balance of Ni and trace elements, wherein the sum of the components is 100 percent; the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube is controlled and limited by components, a certain amount of elements such as Co, Mo and B are added, the smelting process adopts vacuum induction and vacuum self-consumption, the tube making process adopts hot extrusion and full cold rolling, and finally the solution treatment is carried out.

Description

Novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for power station and manufacturing method
Technical Field
The invention relates to a nickel-chromium-cobalt-molybdenum high-temperature alloy seamless pipe, in particular to a high-temperature alloy seamless pipe for a novel power station heat transfer pipe.
Background
The emission of greenhouse gases is a topic of high importance in all countries in recent years, and the system for increasing the recovered emission of the traditional power plant is very complex and expensive, and can greatly increase the power generation cost. New technologies, if able to provide a cheap, clean and flexible source of electricity to the grid, are easier to adjust the amount of electricity on demand than standard solar and wind power plants. The Alam cycle technology named by Rodney Allam, Engineer in England abandons the traditional thermal power CO2Combustion, using no steam to drive the generator, and using pressure to make CO2And the supercritical state is realized, so that the turbine of the generator realizes high-speed rotation. Remaining pure CO2The gas can be reused or buried underground, and the water vapor condenses into clean water. During the whole circulation, CO2Conducting internally, which means that there are no solid dust particles, mercury or sulphur oxides. The natural gas power station utilizing the Alam cycle has very high heat conversion efficiency, and can convert 80% of natural gas energy into electric energy (most advanced natural gas power stations can only achieve 60%). CO 22The discharge amount is 0.4kg/kwh, which is far lower than the discharge amount of 8kg/kwh of a common coal-fired power plant. The cost of electricity generation is equivalent to 6 cents per degree of electricity, and is equivalent to other gas turbines. The technology also encloses ' ten major breakthroughs in the world ' science and technology review of Ma province science and technology ' in 2018. The project process currently known is that an exemplary plant of natural gas in laports, texas, usa has been successfully fired in 2018 in 5 months, the size of the exemplary plant being only 50 megawatts smaller. According to the planning, if the pilot plant can fully operate and output power (rated power 25 MW), the power of the American society is expanded to 300 megawatts in 2021, the scale of a full-size power station is built, the building cost is 3 hundred million dollars, and the prospect is optimistic.
The excellent corrosion resistance of the high-temperature alloys of the nickel-chromium-cobalt-molybdenum system in hot-corrosion applications, such as in sulfidisation environments, in particular in oxidation and carburization environments with cycles up to 1100 ℃, combined with excellent mechanical properties, makes them particularly suitable for use in high-temperature applications. Has good instantaneous and long-term mechanical properties at high temperature of up to 1100 ℃, and can be widely applied to industrial and aviation turbine parts, air heaters, muffle tanks and radiant tubes, high-temperature heat exchangers, valves and springs, and high-temperature gas-cooled nuclear reactors, such as helium/helium medium heat exchangers, chemical equipment, spiral tubes and pipelines in the petrochemical industry, and the like.
The nickel-chromium-cobalt-molybdenum high-temperature alloy has high alloying degree, large deformation resistance and difficult smelting and manufacturing, at present, the nickel-chromium-cobalt-molybdenum high-temperature alloy is in research and small-batch trial production stages abroad, the process reports of the industrial production are less, the nickel-chromium-cobalt-molybdenum high-temperature alloy is always in a blocked state externally, the production of the nickel-chromium-cobalt-molybdenum high-temperature alloy in China has no related report, and the technical parameters of the industrial production are not supported temporarily. Therefore, a nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube which has good high-temperature structure, mechanical stability, corrosion resistance, high dimensional precision and surface quality and can meet the requirements of a novel power station and a preparation process thereof are urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, provide a nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for a novel power station and a manufacturing method thereof, wherein the tube has good organization and mechanical properties, good dimensional accuracy and surface quality, and solve the manufacturing process problem of the nickel-chromium-cobalt-molybdenum high-temperature alloy so as to meet the use requirements of the novel power station.
In order to solve the technical problems, the invention provides a novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for a power station, which comprises the following components in percentage by weight: c: 0.03-0.10%, Si is less than or equal to 1.0%, Mn is less than or equal to 0.70%, P is less than or equal to 0.012%, S is less than or equal to 0.008%, Cr: 20.00-24.00%, Co: 10.00-15.00%, Al: 0.70-1.50%, Ti: 0.20-0.70%, Mo: 8.00-10.00%, Fe is less than or equal to 2.00%, Cu is less than or equal to 0.5%, B: 0.001-0.006 percent of the total weight of the components, less than or equal to 0.005 percent of Pb, less than or equal to 0.005 percent of Sb, less than or equal to 0.001 percent of Bi, less than or equal to 0.010 percent of Sn, less than or equal to 0.010 percent of As, and the balance of Ni and trace elements, wherein the sum of the components is 100 percent.
The invention also designs a manufacturing method of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station, which comprises the following steps:
(one) smelting
The alloy material of the seamless pipe is smelted by vacuum induction at 1500 ℃ +/-10 ℃, cast into an alloy ingot with the diameter of 360 x 2800mm, annealed at 1000-1100 ℃ for 24h x air cooling, then subjected to vacuum self-consumption to form an alloy ingot with the diameter of 423mm, and subjected to homogenization heat treatment, wherein the heat treatment system is as follows: the temperature is 1200-1240 ℃ and 72h, and the cooling mode is air cooling;
(II) forging
Cogging the alloy ingot obtained in the step (I) by adopting a 2000-ton quick forging machine, forging the alloy ingot into a phi 250mm forging blank by using a 1300-ton radial forging machine, wherein the specification of the alloy ingot is 320mm octagonal blank;
(III) Hot extrusion
Peeling the forged blank obtained in the step (II), cutting to length, machining into a hot extrusion blank with the specification of phi 236mm, and then hot extruding into a hot extrusion pipe with the specification of phi 114 multiplied by 12mm at 1150 ℃;
(IV) solution treatment and acid pickling
Carrying out solution heat treatment on the hot extrusion pipe obtained in the step (three) in a high-temperature box type furnace, wherein the heat treatment temperature is 1160-1200 ℃, the heat preservation time is 24-30 min, the cooling mode is water cooling, then straightening is carried out, head and tail defects are cut off and burrs are removed, acid washing is carried out at 50-70 ℃ by adopting 5-8% hydrofluoric acid and 10-15% nitric acid mixed solution, and then washing is carried out to remove residual acid;
(V) pipe end treatment
Inspecting, grinding and polishing the inner surface and the outer surface of the alloy pipe obtained in the step (IV), and then performing 45-degree chamfering treatment on the outer wall of one end of the alloy pipe;
(VI) Cold Rolling and Heat treatment
Performing cold rolling on the alloy pipe processed in the step (five) by adopting an LG110 rolling mill for 2 passes, deoiling after cold rolling of each pass, performing solution heat treatment in a high-temperature box type furnace, and then performing straightening, acid pickling, inner and outer surface inspection, polishing, inner and outer polishing and chamfering treatment;
carrying out cold rolling for 2 passes by adopting an LG60 rolling mill, deoiling after cold rolling for each pass, carrying out solution heat treatment in a high-temperature box type furnace, and then carrying out straightening, acid pickling, inner and outer surface inspection, coping, inner and outer polishing and chamfering treatment;
performing cold rolling for 2 passes by using an LG30 rolling mill, deoiling after each cold rolling, performing solid solution heat treatment in a pure hydrogen protective bright heat treatment furnace, and performing straightening, inner and outer surface inspection, coping, inner and outer polishing and chamfering treatment;
further carrying out 2-pass cold rolling by three-roll LD30 finish rolling, deoiling after each pass cold rolling, carrying out solid solution heat treatment in a pure hydrogen protection bright heat treatment furnace, straightening, inner and outer surface inspection, coping, inner and outer polishing and chamfering the pipe end;
(VII) examination
Carrying out ultrasonic inspection on each finished product pipe, wherein the size of the artificial defect of the ultrasonic inspection standard sample is 0.07mm multiplied by 7mm multiplied by 0.14 mm;
carrying out a hydrostatic test on each finished product pipe, wherein the hydrostatic pressure is 69MPa, and the pressure maintaining time is more than or equal to 5 s;
(eighth) cleaning
Cleaning the outer surface: wiping the outer surface of the alloy pipe with cotton cloth dipped with acetone or alcohol one by one until the outer surface is free from oil stains and color spots caused by foreign matters, and finally wiping the alloy pipe clean with dry white cotton cloth;
cleaning the inner surface: cleaning the wool felt plugs one by dipping with acetone or alcohol and blowing high-pressure nitrogen into the tube holes until the surfaces of the cleaned wool felt plugs are free of oil stains and color spots caused by foreign matters, and finally drying the wool felt plugs or white cotton cloth;
(nine) identification and package
Marking the outer surface of the high-temperature alloy seamless pipe one by adopting a laser code spraying mode;
cleaning each high-temperature alloy seamless pipe after marking, immediately firmly sealing two ends by using plastic plugs after cleaning, sleeving by adopting a pentachloroethylene plastic bag, bundling the high-temperature alloy seamless pipes and then putting into a wooden box.
The technical scheme of the invention is further defined as follows:
furthermore, in the manufacturing method of the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the novel power station, in the step (six), performing cold rolling on the alloy pipe subjected to surface and chamfering treatment by using precise matching of an LG110 cold rolling pass and a core rod for 2 passes, respectively rolling to reach 89 mm multiplied by 9mm and 76 mm multiplied by 7mm, controlling the cold rolling deformation to be 30-45%, feeding 1-4 mm/time, rolling speed to be 30-50 times/min, controlling the outer diameter to be +/-0.60 mm and +/-0.50 mm respectively, controlling the wall thickness to be +/-0.40 mm and +/-0.30 mm respectively, performing solution heat treatment in a high-temperature box furnace after cold rolling and deoiling for each pass, controlling the heat treatment temperature to be 1170-1200 ℃, preserving heat for 12-20 min, cooling by water cooling, controlling the straightness to be not more than 2.0mm/m after straightening, and performing acid washing, inner and outer surface inspection, coping, inner and outer polishing and chamfering treatment for 45 degrees on one end outer wall.
In the manufacturing method of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless pipe for the power station, in the step (VI), the alloy pipe is subjected to 2-pass cold rolling through an LG60 cold rolling pass and precise matching of a core rod, the alloy pipe is respectively rolled to phi 60 multiplied by 5.4mm and phi 38 multiplied by 3.9mm, the cold rolling deformation is 35-55%, the feeding amount is 1-4 mm/time, the rolling speed is 30-50 times/min, the outer diameter is respectively controlled to +/-0.30 mm and +/-0.25 mm, the wall thickness is respectively controlled to +/-0.25 mm and +/-0.20 mm, solution heat treatment is carried out in a high-temperature box furnace after each pass cold rolling and oil removal, the heat treatment temperature is 1170-1200 ℃, the heat preservation is carried out for 6-12 min, the cooling mode is water cooling, the straightness is controlled to be not more than 1.5mm/m after straightening, and then acid cleaning, inner and outer surface inspection, coping, inner and outer polishing are carried out.
In the manufacturing method of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless pipe for the power station, in the step (VI), the alloy pipe is subjected to 2-pass cold rolling through the LG30 cold rolling pass and the precise matching of the core rod, the alloy pipe is respectively rolled to phi 26.8 multiplied by 3.1mm and phi 19 multiplied by 2.65mm, the cold rolling deformation is 40-45%, the feeding amount is 1-3 mm/time, the rolling speed is 20-40 times/min, the outer diameter is respectively controlled to +/-0.18 mm and +/-0.12 mm, the wall thickness is respectively controlled to +/-0.12 mm and +/-0.10 mm, after each cold rolling and oil removal, the solution heat treatment is carried out in a pure hydrogen protection bright heat treatment furnace, the heat treatment temperature is 1170-1200 ℃, the heat preservation is carried out for 6-10 min, the cooling mode is water cooling, the straightness is controlled to be not more than 1.2mm/m after straightening, and then the inner and outer surface inspection, coping, inner and outer polishing and.
In the manufacturing method of the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless pipe for the power station, in the step (VI), the alloy pipe is subjected to 2-pass cold rolling through LD30 three-roll finish rolling pass and precise matching of a core rod, the alloy pipe is respectively rolled to phi 16 multiplied by 2.25mm and phi 12.7 multiplied by 1.85mm, the cold rolling deformation is 25-40%, the feeding amount is 1-3 mm/pass, the rolling speed is 10-30 times/min, the outer diameter is respectively controlled to +/-0.08 mm and +/-0.05 mm, the wall thickness is respectively controlled to +/-0.08 mm and +/-0.06 mm, solution heat treatment is carried out in a pure hydrogen protection bright heat treatment furnace after each cold rolling and deoiling, the heat treatment temperature is 1140-1170 ℃, the heat preservation is 5-10 min, the cooling mode is water jacket cooling, straightening is carried out, the straightness is controlled to be less than or equal to 1.0mm/m after straightening, and then internal and external surface inspection, grinding, internal and external polishing and chamfering.
In the manufacturing method of the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the novel power station, the allowable deviation of the outer diameter of the manufactured seamless tube is +/-0.05 mm, and the allowable deviation of the wall thickness is +/-0.10 mm; the roughness Ra of the inner surface and the outer surface is less than or equal to 1.0 mu m; the grain size is 3-7 grade; the room temperature mechanical properties are as follows: rm≥680MPa，Rp0.2≥240MPa，A50≥40%，RmDenotes tensile strength, Rp0.2Denotes the yield strength, A50Representing the elongation after fracture;
high-temperature mechanical properties: at 100 ℃, Rm≥670MPa，Rp0.2R is more than or equal to 212MPa at 200 DEG Cm≥655MPa，Rp0.2At 300 ℃ and under the pressure of more than or equal to 188MPa, Rm≥647MPa，Rp0.2R is not less than 174MPa at 400 DEG Cm≥624MPa，Rp0.2R is more than or equal to 166MPa at 500 DEG Cm≥607MPa，Rp0.2R is not less than 162MPa at 600 DEG Cm≥580MPa，Rp0.2R is not less than 150MPa at 700 DEG Cm≥500MPa，Rp0.2≥145Mpa。
The invention has the beneficial effects that:
(1) the high-temperature alloy seamless pipe of the invention is prepared by selectively adding alloy elements such as Cr: 20.00-24.00%, Co: 10.00-15.00%, Al: 0.70-1.50%, Ti: 0.20-0.70%, Mo: 8.00-10.00%, B: 0.001-0.006%, etc., wherein:
al and Ti: a small amount of gamma 'phase (Ni 3 (Al, Ti) with the mass fraction of 4-5%) is formed to be precipitated and strengthened, and the gamma' phase is an important strengthening phase in the nickel-based alloy and has a face-centered cubic superlattice structure;
ni and Cr: the mass fraction is large, so that the alloy has strong corrosion resistance;
al and Cr: the combined action of the components enables the composite material to have stronger high-temperature oxidation resistance;
co and Mo: the solid solution strengthening effect is achieved, and the alloy is easy to form and weld;
b: microalloying, improving creep strength and plasticity of the alloy.
(2) According to the invention, 8-pass cold rolling deformation is adopted in the forming process, the deformation amount of each pass is controlled to be 25-55%, if the deformation amount exceeds 55%, the alloy pipe has the risk of cracking in the rolling process, and if the deformation amount is less than 25%, the deformation amount is too small, the grain size range is increased after the solution heat treatment, the structure uniformity of the alloy pipe is influenced, and further the performance uniformity of the alloy pipe is influenced; the feeding amount of the 1 st to 4 th pass is controlled to be 1 to 4 mm/time, the rolling speed is 30 to 50 times/min, the uneven deformation of the alloy pipe can be effectively prevented, and the obtained alloy pipe is good in surface quality and small in size deviation; the feeding amount of the 5 th to 6 th pass is controlled to be 1-3 mm/time, the rolling speed is controlled to be 20-40 times/min, and the surface quality and the dimensional accuracy of the alloy pipe are further improved; the feeding amount of the 7 th to 8 th pass is controlled to be 1 to 3 mm/time, the rolling speed is 10 to 30 times/min, the surface quality of the alloy pipe reaches the optimal degree, and the dimensional accuracy is higher.
(3) In the step (V) and the step (VI), before cold rolling, the outer wall of one end of each pass of the alloy pipe is required to be subjected to chamfering treatment, so that the stress concentration phenomenon is reduced when the alloy pipe is subjected to cold rolling, and the head part is prevented from cracking to influence the product quality.
(4) The novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station is characterized in that the alloy tube in the 1 st to 6 th passes is subjected to solution heat treatment by using a high-temperature box type furnace, the heat treatment temperature is 1170-1200 ℃, the temperature is higher, so that the alloy tube has better plasticity, the forming in the later process is facilitated, the alloy tube in the 7 th to 8 th passes is subjected to solution heat treatment by using a pure hydrogen protection bright heat treatment furnace, the heat treatment temperature is 1140-1170 ℃, the temperature is gradually reduced, so that the alloy tube has good tissue and comprehensive mechanical properties, and the good surface quality of the alloy tube is ensured.
The cold rolling deformation of the alloy material after solution treatment does not exceed 55 percent, otherwise, the alloy material has cracking risk, but in order to ensure that the material can recover and recrystallize the structure after deformation and heat treatment and simultaneously consider the influence of the uniformity of the structure after the outer diameter and the wall thickness of the cold rolling are reduced, the adopted cold rolling deformation is strictly controlled within the range of 25-55 percent.
The invention relates to a 45-degree chamfering treatment of the outer wall of a pipe end: because the alloy is more severe in work hardening than stainless steel, the head part is easy to generate stress concentration phenomenon during cold rolling, and the alloy pipe needs to be subjected to chamfering treatment of 45 degrees on the outer wall of the pipe end before each pass of cold rolling so as to avoid cracking caused by stress concentration during the cold rolling of the head part and influence on the surface quality of the pipe.
The alloy seamless tube is subjected to cold rolling for 8 passes, and solution heat treatment is carried out in a high-temperature box type furnace after the first 4 cold rolling passes so as to ensure that the alloy tube has sufficient tissue heat treatment, has better plasticity, is convenient for later cold rolling, and gradually eliminates the uneven outer diameter and the uneven wall thickness of the hot extruded tube. After pure hydrogen protective bright heat treatment is adopted in the last 4 passes, the surface quality of the alloy pipe is good, acid washing is not needed, and meanwhile, the size deviation and the surface roughness of the alloy pipe are controlled in a smaller range.
The alloy seamless tube is a small-caliber heat exchange tube, has high surface quality requirement, and has good requirements and results on size deviation, surface roughness and the like after heat treatment by adopting a pure hydrogen protective bright heat treatment furnace.
In conclusion, the manufacturing method adopts the processes of vacuum induction, vacuum consumable smelting, hot extrusion and cold rolling for forming, accurately controls the components of the alloy pipe, and effectively controls the non-metallic inclusions, so that the alloy pipe has good structure, high-temperature strength and corrosion resistance, and the structure and the performance completely meet the use requirements of the high-temperature alloy seamless pipe for the novel power station heat transfer pipe.
Drawings
FIG. 1 is a flow chart of the manufacturing process of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station.
Detailed Description
Example 1
The embodiment provides a novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for a power station, which comprises the following components in percentage by weight: c: 0.062%, Si: 0.012%, Mn: 0.03%, P: 0.005%, S: 0.002%, Cr: 22.82%, Co: 12.95%, Al: 1.21%, Ti: 0.43%, Mo: 8.78%, Fe: 0.18%, Cu: 0.0089%, B: 0.005%, Pb: 0.001%, Sb: 0.001%, Bi: 0.001%, Sn: 0.005%, As: 0.005 percent, and the balance of Ni and trace elements, wherein the sum of the components is 100 percent.
The process of the manufacturing method of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station is shown in figure 1, and the manufacturing method specifically comprises the following steps:
(one) smelting
The alloy material of the seamless pipe is smelted by vacuum induction at 1500 ℃ +/-10 ℃, cast into an alloy ingot with the diameter of 360 x 2800mm, annealed at 1000-1100 ℃ for 24h x air cooling, then subjected to vacuum self-consumption to form an alloy ingot with the diameter of 423mm, and subjected to homogenization heat treatment, wherein the heat treatment system is as follows: the temperature is 1200-1240 ℃ multiplied by 72h, and the cooling mode is air cooling, so that the segregation degree of alloy elements can be reduced;
(II) forging
The alloy ingot obtained in the step (I) is cogging by adopting a 2000-ton quick forging machine, an octagonal blank with the specification of 320mm is forged into a phi 250mm forged blank by adopting a 1300-ton radial forging machine, so that the defects of casting state looseness and the like generated in the smelting process of the alloy can be eliminated, the microstructure is more compact, and the performance is more excellent;
(III) Hot extrusion
Peeling the forged blank obtained in the step (II) to remove oxide skin and other defects, then cutting to length, machining into a hot extrusion blank with the specification of phi 236mm, and then hot extruding into a hot extrusion pipe with the specification of phi 114 multiplied by 12mm at 1150 ℃, wherein the alloy has the best high-temperature thermoplasticity at the temperature, the hot extrusion structure is more uniform, and the mechanical property is good;
(IV) solution treatment and acid pickling
Carrying out solution heat treatment on the hot extrusion pipe obtained in the step (three) in a high-temperature box type furnace, wherein the heat treatment temperature is 1160-1200 ℃, the heat preservation time is 24-30 min, the cooling mode is water cooling, then straightening is carried out, head and tail defects are cut off and burrs are removed, acid washing is carried out at 50-70 ℃ by adopting 5-8% hydrofluoric acid and 10-15% nitric acid mixed solution, and then washing is carried out to remove residual acid;
(V) pipe end treatment
Inspecting, grinding and polishing the inner surface and the outer surface of the alloy pipe obtained in the step (IV), and then performing 45-degree chamfering treatment on the outer wall of one end of the alloy pipe;
(VI) Cold Rolling and Heat treatment
And (5) carrying out cold rolling on the alloy pipe treated in the step (five) for 2 passes by adopting an LG110 rolling mill:
respectively rolling to phi 89 multiplied by 9mm and phi 76 multiplied by 7mm, controlling the cold rolling deformation amount to be 30-45%, feeding amount to be 1-4 mm/time, rolling speed to be 30-50 times/min, respectively controlling the outer diameter to be +/-0.60 mm and +/-0.50 mm, respectively controlling the wall thickness to be +/-0.40 mm and +/-0.30 mm, respectively carrying out solution heat treatment in a high-temperature box furnace after each pass of cold rolling and after deoiling, wherein the heat treatment temperature is 1170-1200 ℃, keeping the temperature for 12-20 min, cooling by water, controlling the straightness to be less than or equal to 2.0mm/m after straightening, and then carrying out acid cleaning, inner and outer surface inspection, coping, inner and outer polishing and chamfering treatment at 45 degrees at one end so as to reduce the stress concentration phenomenon during the cold rolling of the alloy pipe and prevent the head from cracking;
carrying out cold rolling for 2 passes by adopting an LG60 rolling mill:
respectively rolling to phi 60 multiplied by 5.4mm and phi 38 multiplied by 3.9mm, wherein the cold rolling deformation is 35-55%, the feeding amount is 1-4 mm/time, the rolling speed is 30-50 times/min, so as to obtain better dimensional accuracy, the outer diameter is respectively controlled to +/-0.30 mm and +/-0.25 mm, the wall thickness is respectively controlled to +/-0.25 mm and +/-0.20 mm, after each pass of cold rolling and oil removal, solution heat treatment is carried out in a high-temperature box furnace, the heat treatment temperature is-1200 ℃, the temperature is kept for 6-12 min, the cooling mode is water cooling, after straightening, the straightness is controlled to be less than or equal to 1.5mm/m, then acid washing, inner and outer surface inspection, coping, inner and outer polishing, inner and outer chamfering are carried out, one end of the alloy pipe is subjected to 45-degree 1170 chamfering treatment, so that the stress concentration phenomenon is reduced when the cold rolling is carried;
and then carrying out 2-pass cold rolling by adopting an LG30 rolling mill:
respectively rolling to form phi 26.8 multiplied by 3.1mm and phi 19 multiplied by 2.65mm, wherein the cold rolling deformation is 40-45%, the feeding amount is 1-3 mm/time, the rolling speed is 20-40 times/min, so as to obtain better dimensional accuracy, the outer diameter is respectively controlled to be +/-0.18 mm and +/-0.12 mm, the wall thickness is respectively controlled to be +/-0.12 mm and +/-0.10 mm, after each pass of cold rolling and oil removal, solution heat treatment is carried out in a pure hydrogen protection bright heat treatment furnace, the heat treatment temperature is 1170-1200 ℃, the heat preservation is carried out for 6-10 min, the cooling mode is water cooling, the straightness is controlled to be less than or equal to 1.2mm/m after straightening, then internal and external surface inspection, grinding, internal and external polishing and chamfering treatment with 45 degrees at one end are carried out, so that the stress concentration phenomenon is reduced when the alloy pipe is subjected to cold rolling, and the head is;
further adopting LD30 three-roller finish rolling to carry out 2-pass cold rolling:
respectively rolling to phi 16 multiplied by 2.25mm and phi 12.7 multiplied by 1.85mm, wherein the cold rolling deformation is 25-40%, the feeding amount is 1-3 mm/time, the rolling speed is 10-30 times/min, so as to obtain better dimensional accuracy, the outer diameter is respectively controlled to +/-0.08 mm and +/-0.05 mm, the wall thickness is respectively controlled to +/-0.08 mm and +/-0.06 mm, after cold rolling and deoiling in each pass, solution heat treatment is carried out in a pure hydrogen protection bright heat treatment furnace, the heat treatment temperature is 1140-1170 ℃, the heat preservation is carried out for 5-10 min, the cooling mode is water jacket cooling, then straightening is carried out, the straightness is controlled to be less than or equal to 1.0mm/m after straightening, then internal and external surface inspection, coping, internal and external polishing are carried out, and the pipe end is chamfered;
(VII) examination
Performing ultrasonic inspection on each finished tube, wherein the size of the artificial defect of the ultrasonic detection standard sample is 0.07mm multiplied by 7mm multiplied by 0.14mm (depth multiplied by length multiplied by width);
carrying out a hydrostatic test on each finished product pipe, wherein the hydrostatic pressure is 69MPa, and the pressure maintaining time is more than or equal to 5 s;
performing surface inspection and dimension inspection on each finished product pipe, wherein the surface roughness Ra is less than or equal to 1.0 mu m, the allowable deviation of the outer diameter is +/-0.05 mm, and the allowable deviation of the wall thickness is +/-0.10 mm;
(eighth) cleaning
Cleaning the outer surface: wiping the outer surface of the alloy pipe with cotton cloth dipped with acetone or alcohol one by one until the outer surface is free from oil stains and color spots caused by foreign matters, and finally wiping the alloy pipe clean with dry white cotton cloth;
cleaning the inner surface: cleaning the wool felt plugs one by dipping with acetone or alcohol and blowing high-pressure nitrogen into the tube holes until the surfaces of the cleaned wool felt plugs are free of oil stains and color spots caused by foreign matters, and finally drying the wool felt plugs or white cotton cloth;
(nine) identification and package
Marking the outer surface of the high-temperature alloy seamless pipe one by adopting a laser code spraying mode instead of ink code spraying mode marking;
cleaning each high-temperature alloy seamless pipe after marking, immediately firmly sealing two ends by using a plastic plug after cleaning, sleeving by using a pentachloroethylene plastic bag, bundling the high-temperature alloy seamless pipes, putting the bundled high-temperature alloy seamless pipes into a wooden box, wherein the wooden box is firm enough, a proper amount of drying agent is put into a proper position according to the quantity of packaging steel pipes and the volume design of the packaging wooden box, the drying agent is strictly forbidden to be in direct contact with the pipes, the halogen or sulfur content of packaging materials (such as a sealing bag, the plastic plug and the like) is less than 0.10 percent (weight percentage), and the surface of the alloy pipe after sealed packaging is covered with a layer of plastic film to prevent the packaging bag from being; after the wooden box is packed, a packing list is attached to the wooden box to indicate the name or trademark of a manufacturing plant, the material brand, the specification, the smelting furnace number, the batch number (production batch number) of a heat treatment furnace, the steel pipe number and the like, a mark is attached to the outside of the wooden box, a hoisting part, a balance center mark and a transportation warning mark are indicated at a striking position outside the wooden box, such as marks of 'carefully placing lightly', 'keeping dry', 'the face upwards', 'forbidding a forklift', and the like, and the wooden box cannot be opened during the loading and transporting process is indicated.
The roughness Ra of the inner surface and the outer surface of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station manufactured by the embodiment is less than or equal to 0.8 mu m; the outer diameter is +/-0.03 mm, and the wall thickness is +/-0.04; the grain size is 5.5 grade; room temperature mechanical properties: rm=810MPa，Rp0.2=358MPa，A50=58.5%，RmDenotes tensile strength, Rp0.2Denotes the yield strength, A50Representing the elongation after fracture; microscopic Vickers hardness HV at room temperature0.5=203, 207, 209; high-temperature tensile property: at 100 ℃, Rm=744MPa，Rp0.2=297MPa，A50=50.5%, R at 200 ℃m=719MPa，Rp0.2=267MPa，A50=48.5%, R at 300 ℃m=684MPa，Rp0.2=248MPa，A50=42.5%, R at 400 ℃m=674MPa，Rp0.2=225MPa，A50=44.0%, R at 500 ℃m=650MPa，Rp0.2=229MPa，A50=42.5%, R at 550 ℃m=623MPa，Rp0.2=226MPa，A50=43.5%, R at 600 ℃m=611MPa，Rp0.2=212MPa，A50=45.5%, R at 650 DEG Cm=586MPa，Rp0.2=205MPa，A50=41.5%, R at 700 DEG Cm=514MPa，Rp0.2=211MPa，A50=36.5%。
Example 2
The embodiment provides a novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for a power station, which comprises the following components in percentage by weight: c: 0.063%, Si: 0.014%, Mn: 0.032%, P: 0.004%, S: 0.003%, Cr: 22.81%, Co: 12.93%, Al: 1.20%, Ti: 0.44%, Mo: 8.77%, Fe: 0.181%, Cu: 0.01%, B: 0.005%, Pb: 0.001%, Sb: 0.001%, Bi: 0.001%, Sn: 0.004%, As: 0.004 percent, and the balance of Ni and trace elements, wherein the sum of the components is 100 percent.
The manufacturing method of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station in the embodiment 1 is adopted, and the roughness Ra of the inner surface and the outer surface of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station manufactured by the same manufacturing method is less than or equal to 0.7 mu m; the outer diameter is +/-0.02 mm, and the wall thickness is +/-0.05; the grain size is 5.5 grade; room temperature forceChemical properties: rm=815MPa，Rp0.2=359MPa，A50=59.0%，RmDenotes tensile strength, Rp0.2Denotes the yield strength, A50Representing the elongation after fracture; microscopic Vickers hardness HV at room temperature0.5=204, 205, 206; high-temperature tensile property: at 100 ℃, Rm=746MPa，Rp0.2=299MPa，A50=51.0%, R at 200 ℃m=721MPa，Rp0.2=269MPa，A50=48.0%, R at 300 ℃m=688MPa，Rp0.2=249MPa，A50=42.5%, R at 400 ℃m=678MPa，Rp0.2=226MPa，A50=44.5%, R at 500 ℃m=653MPa，Rp0.2=231MPa，A50=42.0%, R at 550 ℃m=625MPa，Rp0.2=227MPa，A50=43.5%, R at 600 ℃m=614MPa，Rp0.2=214MPa，A50=45.0%, R at 650 DEG Cm=588MPa，Rp0.2=211MPa，A50=42.0%, R at 700 DEG Cm=513MPa，Rp0.2=213MPa，A50=37.0%。
Example 3
The embodiment provides a novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for a power station, which comprises the following components in percentage by weight: c: 0.063%, Si: 0.014%, Mn: 0.032%, P: 0.004%, S: 0.003%, Cr: 22.81%, Co: 12.93%, Al: 1.20%, Ti: 0.44%, Mo: 8.77%, Fe: 0.181%, Cu: 0.01%, B: 0.005%, Pb: 0.001%, Sb: 0.001%, Bi: 0.001%, Sn: 0.004%, As: 0.004 percent, and the balance of Ni and trace elements, wherein the sum of the components is 100 percent.
The manufacturing method of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station in the embodiment 1 is adopted, and the roughness Ra of the inner surface and the outer surface of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station manufactured by the same manufacturing method is less than or equal to 0.8 mu m; the outer diameter is +/-0.04 mm, and the wall thickness is +/-0.04; the grain size is 5.5 grade; room temperature mechanical properties: rm=818MPa，Rp0.2=356MPa，A50=58.5%，RmDenotes tensile strength, Rp0.2Denotes the yield strength, A50After showing the disconnectionElongation percentage; microscopic Vickers hardness HV at room temperature0.5=204, 203, 207; high-temperature tensile property: at 100 ℃, Rm=744MPa，Rp0.2=295MPa，A50=51.5%, R at 200 ℃m=720MPa，Rp0.2=267MPa，A50=48.5%, R at 300 ℃m=687MPa，Rp0.2=247MPa，A50=43.0%, 400 ℃, Rm =677MPa, rp0.2=225MPa, a50=44.0%, 500 ℃, Rm =652MPa, rp0.2=228MPa, a50=42.5%, 550 ℃, Rm =623MPa, rp0.2=224MPa, a50=44.0%, 600 ℃, Rm =613MPa, rp0.2=212MPa, a50=45.5%, 650 ℃, Rm =585MPa, rp0.2=210MPa, a50=42.5%, 700 ℃, Rm =512MPa, rp0.2=214MPa, a50= 37.5%.
The alloy material in the embodiment has better cold working performance, namely the cold rolling deformation can reach 55 percent at most, which is higher than that of a seamless pipe in the prior art;
the seamless tubes obtained in examples 1 to 3 were subjected to a crush test: the test was carried out in two steps, the first step being a ductility test, the sample being pressed to a distance between two plates of H, H = (1+ α) S/(α + S/D), where: h = distance between two plates, mm; s = nominal wall thickness of steel pipe, mm; d = nominal outer diameter of the steel pipe, mm; α = deformation coefficient per unit length, α = 0.09. When the sample is pressed to the distance between the two flat plates, the sample has no crack or split; the second step is an integrity test (closed crush). The alloy tube is continuously flattened until the sample is cracked or the two opposite walls of the sample collide with each other, and the sample does not have visible layering, white spots and impurities during the whole flattening test period; flaring test: according to the GB/T242 specification, a top core with the top core taper of 60 degrees is adopted for carrying out a flaring test, the inner diameter flaring rate is 30 percent, and cracks and splits do not appear after flaring.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.

Claims (7)

1. The novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station is characterized by comprising the following components in percentage by weight: c: 0.03-0.10%, Si is less than or equal to 1.0%, Mn is less than or equal to 0.70%, P is less than or equal to 0.012%, S is less than or equal to 0.008%, Cr: 20.00-24.00%, Co: 10.00-15.00%, Al: 0.70-1.50%, Ti: 0.20-0.70%, Mo: 8.00-10.00%, Fe is less than or equal to 2.00%, Cu is less than or equal to 0.5%, B: 0.001-0.006 percent of the total weight of the components, less than or equal to 0.005 percent of Pb, less than or equal to 0.005 percent of Sb, less than or equal to 0.001 percent of Bi, less than or equal to 0.010 percent of Sn, less than or equal to 0.010 percent of As, and the balance of Ni and trace elements, wherein the sum of the components is 100 percent.
2. The manufacturing method of the novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station as claimed in claim 1 is characterized by comprising the following steps:
(one) smelting
The alloy material of the seamless pipe is smelted by vacuum induction at 1500 ℃ +/-10 ℃, cast into an alloy ingot with the diameter of 360 x 2800mm, annealed at 1000-1100 ℃ for 24h x air cooling, then subjected to vacuum self-consumption to form an alloy ingot with the diameter of 423mm, and subjected to homogenization heat treatment, wherein the heat treatment system is as follows: the temperature is 1200-1240 ℃ and 72h, and the cooling mode is air cooling;
(II) forging
Cogging the alloy ingot obtained in the step (I) by adopting a 2000-ton quick forging machine, forging the alloy ingot into a phi 250mm forging blank by using a 1300-ton radial forging machine, wherein the specification of the alloy ingot is 320mm octagonal blank;
(III) Hot extrusion
Peeling the forged blank obtained in the step (II), cutting to length, machining into a hot extrusion blank with the specification of phi 236mm, and then hot extruding into a hot extrusion pipe with the specification of phi 114 multiplied by 12mm at 1150 ℃;
(IV) solution treatment and acid pickling
Carrying out solution heat treatment on the hot extrusion pipe obtained in the step (three) in a high-temperature box type furnace, wherein the heat treatment temperature is 1160-1200 ℃, the heat preservation time is 24-30 min, the cooling mode is water cooling, then straightening is carried out, head and tail defects are cut off and burrs are removed, acid washing is carried out at 50-70 ℃ by adopting 5-8% hydrofluoric acid and 10-15% nitric acid mixed solution, and then washing is carried out to remove residual acid;
(V) pipe end treatment
Inspecting, grinding and polishing the inner surface and the outer surface of the alloy pipe obtained in the step (IV), and then performing 45-degree chamfering treatment on the outer wall of one end of the alloy pipe;
(VI) Cold Rolling and Heat treatment
Performing cold rolling on the alloy pipe processed in the step (five) by adopting an LG110 rolling mill for 2 passes, deoiling after cold rolling of each pass, performing solution heat treatment in a high-temperature box type furnace, and then performing straightening, acid pickling, inner and outer surface inspection, polishing, inner and outer polishing and chamfering treatment;
carrying out cold rolling for 2 passes by adopting an LG60 rolling mill, deoiling after cold rolling for each pass, carrying out solution heat treatment in a high-temperature box type furnace, and then carrying out straightening, acid pickling, inner and outer surface inspection, coping, inner and outer polishing and chamfering treatment;
performing cold rolling for 2 passes by using an LG30 rolling mill, deoiling after each cold rolling, performing solid solution heat treatment in a pure hydrogen protective bright heat treatment furnace, and performing straightening, inner and outer surface inspection, coping, inner and outer polishing and chamfering treatment;
further carrying out 2-pass cold rolling by three-roll LD30 finish rolling, deoiling after each pass cold rolling, carrying out solid solution heat treatment in a pure hydrogen protection bright heat treatment furnace, straightening, inner and outer surface inspection, coping, inner and outer polishing and chamfering the pipe end;
(VII) examination
Carrying out ultrasonic inspection on each finished product pipe, wherein the size of the artificial defect of the ultrasonic inspection standard sample is 0.07mm multiplied by 7mm multiplied by 0.14 mm;
carrying out a hydrostatic test on each finished product pipe, wherein the hydrostatic pressure is 69MPa, and the pressure maintaining time is more than or equal to 5 s;
(eighth) cleaning
Cleaning the outer surface: wiping the outer surface of the alloy pipe with cotton cloth dipped with acetone or alcohol one by one until the outer surface is free from oil stains and color spots caused by foreign matters, and finally wiping the alloy pipe clean with dry white cotton cloth;
cleaning the inner surface: cleaning the wool felt plugs one by dipping with acetone or alcohol and blowing high-pressure nitrogen into the tube holes until the surfaces of the cleaned wool felt plugs are free of oil stains and color spots caused by foreign matters, and finally drying the wool felt plugs or white cotton cloth;
(nine) identification and package
Marking the outer surface of the high-temperature alloy seamless pipe one by adopting a laser code spraying mode;
cleaning each high-temperature alloy seamless pipe after marking, immediately firmly sealing two ends by using plastic plugs after cleaning, sleeving by adopting a pentachloroethylene plastic bag, bundling the high-temperature alloy seamless pipes and then putting into a wooden box.
3. The novel method for manufacturing the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station as claimed in claim 2, wherein the method comprises the following steps: in the step (VI), the alloy pipe after surface and chamfer treatment is subjected to cold rolling for 2 passes through precise matching of an LG110 cold rolling pass and a core rod, the alloy pipe is respectively rolled to a diameter of 89 multiplied by 9mm and a diameter of 76 multiplied by 7mm, the cold rolling deformation is controlled to be 30-45%, the feeding amount is 1-4 mm/time, the rolling speed is 30-50 times/min, the outer diameter is respectively controlled to be +/-0.60 mm and +/-0.50 mm, the wall thickness is respectively controlled to be +/-0.40 mm and +/-0.30 mm, solution heat treatment is carried out in a high-temperature box furnace after each pass of cold rolling and oil removal, the heat treatment temperature is 1170-1200 ℃, the heat preservation is 12-20 min, the cooling mode is water cooling, the straightness is controlled to be less than or equal to 2.0mm/m, and straightening, inner and outer surface inspection, coping, inner and outer polishing and chamfering treatment of 45 degrees on one end.
4. The novel method for manufacturing the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station as claimed in claim 3, wherein the method comprises the following steps: in the step (VI), the alloy pipe is subjected to cold rolling for 2 passes through precise matching of an LG60 cold rolling pass and a core rod, the alloy pipe is respectively rolled to be phi 60 multiplied by 5.4mm and phi 38 multiplied by 3.9mm, the cold rolling deformation is 35-55%, the feeding amount is 1-4 mm/time, the rolling speed is 30-50 times/min, the outer diameter is respectively controlled to be +/-0.30 mm and +/-0.25 mm, the wall thickness is respectively controlled to be +/-0.25 mm and +/-0.20 mm, solution heat treatment is carried out in a high-temperature box type furnace after cold rolling and oil removal of each pass, the heat treatment temperature is 1170-1200 ℃, the heat preservation is carried out for 6-12 min, the cooling mode is water cooling, the straightness is controlled to be less than or equal to 1.5mm/m after straightening, and then acid cleaning, inner and outer surface inspection, grinding, inner and outer polishing and chamfering treatment with 45 degrees.
5. The novel method for manufacturing the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station as claimed in claim 4, wherein the method comprises the following steps:
in the step (VI), the alloy pipe is subjected to cold rolling for 2 passes through precise matching of an LG30 cold rolling pass and a core rod, the alloy pipe is respectively rolled to be 26.8 multiplied by 3.1mm and 19 multiplied by 2.65mm, the cold rolling deformation is 40-45%, the feeding amount is 1-3 mm/time, the rolling speed is 20-40 times/min, the outer diameter is respectively controlled to be +/-0.18 mm and +/-0.12 mm, the wall thickness is respectively controlled to be +/-0.12 mm and +/-0.10 mm, after cold rolling and oil removal of each pass, solution heat treatment is carried out in a pure hydrogen protection bright heat treatment furnace, the heat treatment temperature is 1170-1200 ℃, the heat preservation is carried out for 6-10 min, the cooling mode is water cooling, the straightness is controlled to be less than or equal to 1.2mm/m, and then internal and external surface inspection, polishing, internal and external polishing and chamfering treatment of 45 degrees are carried out on the.
6. The novel method for manufacturing the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station as claimed in claim 5, wherein the method comprises the following steps: in the step (VI), the alloy pipe is subjected to cold rolling for 2 passes through LD30 three-roll finish rolling pass and precise matching of a core rod, the alloy pipe is respectively rolled to phi 16 multiplied by 2.25mm and phi 12.7 multiplied by 1.85mm, the cold rolling deformation is 25-40%, the feeding amount is 1-3 mm/time, the rolling speed is 10-30 times/min, the outer diameter is respectively controlled to +/-0.08 mm and +/-0.05 mm, the wall thickness is respectively controlled to +/-0.08 mm and +/-0.06 mm, after cold rolling and oil removal of each pass, solution heat treatment is carried out in a pure hydrogen protection bright heat treatment furnace, the heat treatment temperature is 1140-1170 ℃, the heat preservation is 5-10 min, the cooling mode is water jacket cooling, then straightening is carried out, the straightness is controlled to be less than or equal to 1.0mm/m after straightening, then inner and outer surface inspection, coping, inner and outer polishing and chamfering are carried out.
7. The novel method for manufacturing the nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for the power station as claimed in claim 6, wherein the method comprises the following steps: the allowable deviation of the outer diameter of the manufactured seamless pipe is +/-0.05 mm, and the allowable deviation of the wall thickness is +/-0.10 mm; the roughness Ra of the inner surface and the outer surface is less than or equal to 1.0 mu m; the grain size is 3-7 grade; the room temperature mechanical properties are as follows: rm≥680MPa，Rp0.2≥240MPa，A50≥40%，RmDenotes tensile strength, Rp0.2Denotes the yield strength, A50Representing the elongation after fracture;
high-temperature mechanical properties: at 100 ℃, Rm≥670MPa，Rp0.2R is more than or equal to 212MPa at 200 DEG Cm≥655MPa，Rp0.2At 300 ℃ and under the pressure of more than or equal to 188MPa, Rm≥647MPa，Rp0.2R is not less than 174MPa at 400 DEG Cm≥624MPa，Rp0.2R is more than or equal to 166MPa at 500 DEG Cm≥607MPa，Rp0.2R is not less than 162MPa at 600 DEG Cm≥580MPa，Rp0.2R is not less than 150MPa at 700 DEG Cm≥500MPa，Rp0.2≥145Mpa。
CN202010534158.2A 2020-06-12 2020-06-12 Novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless tube for power station and manufacturing method Pending CN111636013A (en)

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