CN106282845A - A kind of corrosion-resistant gapless stainless steel tube and preparation method thereof - Google Patents
A kind of corrosion-resistant gapless stainless steel tube and preparation method thereof Download PDFInfo
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- CN106282845A CN106282845A CN201610788689.8A CN201610788689A CN106282845A CN 106282845 A CN106282845 A CN 106282845A CN 201610788689 A CN201610788689 A CN 201610788689A CN 106282845 A CN106282845 A CN 106282845A
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
- C21D1/30—Stress-relieving
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- 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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/10—Modifying the physical properties of iron or steel by deformation by cold working of the whole cross-section, e.g. of concrete reinforcing bars
- C21D7/12—Modifying the physical properties of iron or steel by deformation by cold working of the whole cross-section, e.g. of concrete reinforcing bars by expanding tubular bodies
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- 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
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—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
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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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
Abstract
The invention discloses a kind of corrosion-resistant gapless stainless steel tube and preparation method thereof.By mass percentage, the chemical analysis of this corrosion-resistant gapless stainless steel tube includes: carbon≤0.02%, nitrogen 0.1～0.25%, manganese 1.6～1.8%, chromium 18～20%, nickel 9～11%, silicon 0.3～0.5%, aluminum 1.5～1.7%, tantalum 1.5～2.3%, vanadium 0.3～0.8%, hafnium 1.2～2.6%, titanium 0.5～0.8%, cobalt 0.2～0.4%, tungsten 1.6～3.4%, molybdenum 1～3%, selenium 0.4～0.7%, surplus is ferrum.The present invention with the addition of tantalum, hafnium and tungsten in austenitic stainless steel, and these chemical analysis can improve the corrosion resistance of austenitic stainless steel, hardness, intensity and resistance to elevated temperatures, makes austenitic stainless steel be rich in high ductibility and toughness.
Description
Technical field
The present invention relates to a kind of austenitic stainless steel, be specifically related to a kind of corrosion-resistant gapless stainless steel tube and preparation side thereof
Method.
Background technology
Prepare the seamless steel pipe of conveyance conduit, stainless steel material to be used, but be provided simultaneously with high-strength and high ductility performance and excellent
Very little, traditional ordinary carbon steel and low Cr steel steel are all difficult to meet requirement the stainless steel material of good decay resistance.
Martensitic stain less steel and austenite-ferrite two phase stainless steel is the most generally used to prepare high-strength seamless steel pipe,
Wherein martensitic stain less steel is higher because of carbon containing, therefore has higher intensity, hardness and wearability, but its corrosion resistance is slightly worse, mainly
For preparing the part that mechanical property requirements is higher, corrosion resisting property requirement is general, the application in conveyance conduit then limits relatively
Greatly.
Austenite-ferrite two phase stainless steel is the rustless steel that austenite and ferritic structure respectively account for half.Containing C relatively
In the case of low, Cr content is 18%～28%, and Ni content is 3%～10%.Such steel has austenite and ferrite stainless concurrently
The feature of steel, with ferritic phase ratio, plasticity, toughness are higher, and without brittleness at room temperature, intergranular corrosion resistance performance and welding performance are the most notable
Improving, the 475 DEG C of fragility and the heat conductivity that the most also maintain ferritic stainless steel are high, have the features such as superplasticity.With Austria
Family name's body rustless steel is compared, and intensity height and intergranular corrosion resistance and resistance to chloride stress corrosion are significantly improved.
But the high-load Cr in austenite-ferrite two phase stainless steel can weaken the formation of austenite phase, makes ferritic phase
Becoming the phase constituent taken as the leading factor, this allows for putting down between austenite phase and ferritic phase in austenite-ferrite two phase stainless steel
Weighing apparatus can not get well controlling, and its performance also can be difficult to intended change, often occurs that plasticity is poor, as-welded ductility and anti-corrosion
The shortcomings such as property substantially reduction.
Ultra-low carbon austenitic stainless steel is relatively low because of carbon content ratio, and probability relatively other stainless steel-like materials of intercrystalline corrosion occur
Little, higher Cr, Ni content makes it have excellent anti-CO2、H2S and C1 corrosive nature, and the high temperature high voltage resistant of such steel
Can be good, possess the basic demand preparing conveyance conduit.But it is for needing the conveyance conduit used in harsh corrosive environment, existing
The decay resistance having ultra-low carbon austenitic stainless steel still has much room for improvement.
Summary of the invention
The goal of the invention of the present invention is to provide a kind of ultra-low carbon austenitic stainless steel, solves existing austenitic stainless steel
The problem that decay resistance is relatively low.
A kind of ultra-low carbon austenitic stainless steel, by mass percentage, its chemical analysis includes: carbon≤0.02%, nitrogen 0.1
～0.25%, manganese 1.6～1.8%, chromium 18～20%, nickel 9～11%, silicon 0.3～0.5%, aluminum 1.5～1.7%, tantalum 1.5～
2.3%, vanadium 0.3～0.8%, hafnium 1.2～2.6%, titanium 0.5～0.8%, cobalt 0.2～0.4%, tungsten 1.6～3.4%, molybdenum 1～
3%, selenium 0.4～0.7%, surplus is ferrum.
Carbon content in austenitic stainless steel is arranged on less than 0.02% by the present invention, to prevent intercrystalline corrosion；With
The nitrogen of Shi Tianjia can be collaborative with carbon to make up the rustless steel intensity deficiency problem caused because carbon content reduces, and nitrogen is also Ovshinsky
Body forms element, plays an important role the stability of austenite structure；The addition of nitrogen can also improve the resistance to of austenitic stainless steel
Corrosive nature.
Chromium content in austenitic stainless steel is set slightly above 18% by the present invention, is improving the strong of austenitic stainless steel
While degree, hardness and wearability, it is to avoid high chrome contents affects plasticity and the toughness of austenitic stainless steel.Nickel is as strong austenite
Form element, austenitic stainless steel after mixing with rational ratio with chromium, can be made at room temperature to have stable austenite structure.
Nickel with chromium coordinated, can also improve resistance to stress corrosion resistance, high-temperature oxidation resistance and the intensity of austenitic stainless steel.
Being added with silicon in the austenitic stainless steel of the present invention, it is certain resistance to that silicon can make austenitic stainless steel have concentrated nitric acid
Corrosive power.
The austenitic stainless steel of the present invention is added with aluminum and titanium, aluminum and titanium as ferrite former, suitable
Under addition, evolution reaction can be promoted to occur and form NiTi precipitated phase, aluminum precipitated phase, making austenitic stainless steel strengthen, enter one
Step improves the intensity of austenitic stainless steel.
The austenitic stainless steel of the present invention is added with molybdenum, molybdenum make austenitic stainless steel be resistant to sulphuric acid, phosphoric acid, formic acid,
The corrosion of acetic acid, carbamide etc..
Being added with vanadium and titanium, vanadium and titanium in the austenitic stainless steel of the present invention can chemical combination preferential with carbon, it is to avoid because being formed
Cr23C6And cause Cr depletion zone, it is effectively improved the intergranular corrosion resistance ability of austenitic stainless steel.
The present invention also creatively with the addition of tantalum, hafnium and tungsten in austenitic stainless steel, and wherein tantalum has high anti-corruption
Erosion property, either under cold or heat condition, all will not react with hydrochloric acid, concentrated nitric acid and chloroazotic acid；At 150 DEG C, tantalum
Also will not be corroded by concentrated sulphuric acid and inorganic salt；At normal temperatures, aqueous slkali, chlorine, bromine water, dilute sulfuric acid and other many medicaments
All will not work with tantalum.The addition of tantalum can not only be effectively improved the austenitic stainless steel corrosion-resistant work to all kinds of corrosive substances
With, make austenitic stainless steel be rich in high ductibility and toughness, it is to avoid to produce brittle crack；Tantalum can also form solid solution and carbon with carbon
Compound, with the intergranular corrosion resistance ability that vanadium coordinated improves austenitic stainless steel further；Tantalum can also form solid solution with nitrogen
And nitride, improve decay resistance and the intensity of austenitic stainless steel further.
The addition of hafnium can improve the corrosion resistance of austenitic stainless steel, hardness, intensity and resistance to elevated temperatures equally；And hafnium
Decay resistance and the intensity of austenitic stainless steel with titanium coordinated, can be improved further.
Tungsten can form tungsten carbide with carbon after adding, and tungsten carbide can improve the hardness of austenitic stainless steel, wear-resisting further
Property and resistance to elevated temperatures；And cobalt is not only austenite former, moreover it is possible to work in coordination with tungsten carbide and improve austenite stainless further
The intensity of steel.
Tantalum hafnium, tantalum tungsten, tantalum tungsten hafnium, tantalum tungsten hafnium titanium be collaborative all can improve the intensity of austenitic stainless steel and high temperature resistant further
Performance.
Being added with selenium in the austenitic stainless steel of the present invention, selenium has good heat transfer and electric conductivity, can not only change
The machinability of kind austenitic stainless steel, moreover it is possible to improve the hardness of austenitic stainless steel.
As preferably, by mass percentage, its chemical analysis includes: carbon≤0.02%, nitrogen 0.18～0.22%, manganese
1.72～1.78%, chromium 18.6～19.7%, nickel 9.4～10.8%, silicon 0.36～0.42%, aluminum 1.58～1.65%, tantalum
1.87～2.16%, vanadium 0.54～0.69%, hafnium 1.83～2.24%, titanium 0.66～0.73%, cobalt 0.26～0.32%, tungsten
2.87～3.19%, molybdenum 1.62～2.05%, selenium 0.58～0.64%, surplus is ferrum.
As further preferably, by mass percentage, its chemical analysis includes: carbon 0.017%, nitrogen 0.2%, manganese
1.75%, chromium 19.4%, nickel 10.6%, silicon 0.39%, aluminum 1.62%, tantalum 2.01%, vanadium 0.64%, hafnium 2.13%, titanium
0.69%, cobalt 0.28%, tungsten 3.04%, molybdenum 1.86%, selenium 0.61%, surplus is ferrum.
Another goal of the invention of the present invention is to provide a kind of corrosion-resistant gapless stainless steel tube, and this seamless steel pipe uses described
Ultra-low carbon austenitic stainless steel is prepared from.
Another goal of the invention of the present invention is to provide the preparation method of a kind of described corrosion-resistant gapless stainless steel tube, this system
Preparation Method comprises the following steps:
S1: each raw material of described ultra-low carbon austenitic stainless steel is placed in electric furnace or converter after carrying out just refining and carries out essence
Refining, by acquisition refining liquid continuous casting or be molded into steel billet；
S2: under argon atmosphere, selects ingot shape that described steel billet is carried out electroslag remelting, quickly cools down acquisition after remelting
Ingot casting；
S3: described ingot casting is carried out homogenizing anneal；
S4: the ingot casting after homogenizing anneal is heated to 1100-1250 DEG C, is incubated more than 30min, carries out many to ingot casting
Passage is forged, and makes forging stock；
S5: strip off the skin centering and perforation process to described forging stock, makes pipe；
S6: described pipe is carried out hot extrusion, makes seamless tube blank；
S7: described seamless tube blank is carried out solution treatment；
S8: the seamless tube blank after solution treatment is carried out cold deformation process, makes the contraction percentage of area control 20～40%
Between, it is thus achieved that gapless stainless steel tube semi-finished product；
S9: described seamless pipe semi-finished product are carried out stress relief annealing, the most qualified after obtain described corrosion-resistant seamless not
Rust steel pipe finished product.
As preferably, in step S1, described just refining includes:
S1-1: by the mass percent preset, manganese, nickel, chromium, molybdenum, selenium, aluminum and ferrum are placed in electric furnace or converter,
Melting is carried out at 1350-1420 DEG C, the most melted to all the components, it is thus achieved that melting liquid A；
S1-2: by the mass percent preset, tantalum, hafnium, titanium, tungsten, vanadium and cobalt are placed in electric furnace or converter, 1480～
Melting is carried out at 1620 DEG C, the most melted to all the components, it is thus achieved that melting liquid B；
S1-3: melting liquid B is warming up to 1550-1750 DEG C, and by the mass percent preset, add in melting liquid B
Carbon, nitrogen and silicon, continue melting 3～4h, it is thus achieved that melting liquid C；
S1-4: joined by melting liquid A in the melting liquid C of 1550-1750 DEG C, be heated to 1650～1850 DEG C, is incubated 30
～60min, it is thus achieved that just refine liquid.
The present invention is individually by the melting together with cobalt of tantalum, hafnium, titanium, tungsten, vanadium, and by preferential for melting liquid B and carbon, nitrogen and silicon
Melting together, at a proper temperature, makes carbon, nitrogen preferential and tantalum, hafnium, titanium, tungsten, vanadium and silicon forms solid solution, carbide and nitrogen
Compound, mixes melting liquid C and melting liquid A acquisition the most again and just refines liquid, it is to avoid because carbon forms carbide with chromium, intergranular occurs
Corrosion.
As preferably, in step S1, described refine includes: be placed in AOD furnace, described just refining liquid in 1800～1950 DEG C
Under carry out refine, be incubated 2～2.5h, it is thus achieved that described refining liquid.
As preferably, in step S3, described homogenizing anneal includes with the next stage:
First stage: described ingot casting is heated to 1150～1200 DEG C, it is incubated 10～13h；
Second stage: from 1150～1200 DEG C, annealing temperature is warming up to 1300～1350 DEG C, is incubated 8～11h；
Phase III: annealing temperature is down to 1250～1280 DEG C from 1300～1350 DEG C, it is incubated 10～12h；
Fourth stage: from 1250～1280 DEG C, annealing temperature is down to 1150～1200 DEG C, is incubated 4～6h.
Homogenizing anneal is divided into four-stage by the present invention, is gradually lowered after annealing temperature being gradually risen, can not only
Effectively eliminate component segregation, moreover it is possible to avoid firm Quality Down and high energy consumption problem that long heating environment caused；Make
While all kinds of solid solution and carbide incorporate in austenite structure, it is to avoid stay at solid solution and carbide shared position originally
Lower cavity, forms micro-flaw.
As preferably, in step S6, described hot extrusion comprises the following steps:
S6-1: described pipe is placed in annular furnace preheating, and annular furnace temperature is set to 1050～1100 DEG C, the time in stove
For 1.4d min, wherein d is the wall thickness of described pipe；
S6-2: being placed in induction furnace by the pipe after preheating and once heat, induction furnace temperature is 1150～1180 DEG C,
Insulation 2～4min；
S6-3: once after heating, utilize glass dust that the surfaces externally and internally of pipe is lubricated；
S6-4: after lubrication, carries out expanding process to pipe；
S6-5: after expanding, is placed in pipe in induction furnace and carries out post bake, and induction furnace temperature is 1230～1260 DEG C,
Insulation 2～5min；
S6-6: after post bake, is squeezed into seamless tube blank, air cooling by pipe.
As preferably, in step S7, described solution treatment is: described seamless tube blank is heated to 1050～1150 DEG C, protects
Water-cooled after temperature 10～30min.
Compared with prior art, the invention have the benefit that
(1) carbon content in austenitic stainless steel is arranged on less than 0.02% by the present invention, to prevent intercrystalline corrosion；
The nitrogen simultaneously added can be collaborative with carbon to make up the rustless steel intensity deficiency problem caused because carbon content reduces, and nitrogen is also difficult to understand
Family name's body forms element, plays an important role the stability of austenite structure；The addition of nitrogen can also improve austenitic stainless steel
Decay resistance；
(2) the chromium content in austenitic stainless steel is set slightly above 18% by the present invention, is improving austenitic stainless steel
Intensity, hardness and wearability while, it is to avoid high chrome contents affects plasticity and the toughness of austenitic stainless steel；Nickel is as strong difficult to understand
Family name's body forms element, and austenitic stainless steel can be made after mixing with rational ratio with chromium at room temperature to have stable austenite group
Knit；Nickel with chromium coordinated, can also improve resistance to stress corrosion resistance, high-temperature oxidation resistance and the intensity of austenitic stainless steel；
(3) being added with silicon in the austenitic stainless steel of the present invention, silicon can make austenitic stainless steel have concentrated nitric acid necessarily
Corrosion resistance；
(4) austenitic stainless steel of the present invention is added with aluminum and titanium, aluminum and titanium as ferrite former, suitably
Addition under, evolution reaction can be promoted to occur and form NiTi precipitated phase, aluminum precipitated phase, making austenitic stainless steel strengthen, enter
One step improves the intensity of austenitic stainless steel；
(5) being added with vanadium and titanium, vanadium and titanium in the austenitic stainless steel of the present invention can chemical combination preferential with carbon, it is to avoid because being formed
Cr23C6And cause Cr depletion zone, it is effectively improved the intergranular corrosion resistance ability of austenitic stainless steel；
(6) present invention also creatively with the addition of tantalum in austenitic stainless steel, and the addition of tantalum can not only be effectively improved Austria
The corrosion-resistant effect to all kinds of corrosive substances of family name's body rustless steel, makes austenitic stainless steel be rich in high ductibility and toughness, it is to avoid
Produce brittle crack；Tantalum can also form solid solution and carbide with carbon, improves austenitic stainless steel further with vanadium coordinated
Intergranular corrosion resistance ability；Tantalum can also form solid solution and nitride with nitrogen, improves further and improves the resistance to of austenitic stainless steel
Corrosive nature and intensity；
(7) present invention also creatively with the addition of hafnium, tungsten and cobalt in austenitic stainless steel, and the addition of hafnium can improve Ovshinsky
The stainless corrosion resistance of body, hardness, intensity and resistance to elevated temperatures, and hafnium can improve Ovshinsky further with titanium coordinated
The stainless decay resistance of body and intensity；Tungsten can form tungsten carbide with carbon after adding, and tungsten carbide can improve Ovshinsky further
The stainless hardness of body, wearability and resistance to elevated temperatures；And cobalt is not only austenite former, moreover it is possible to tungsten carbide work in coordination with into
One step improves the intensity of austenitic stainless steel；Moreover, tantalum and hafnium, tantalum and tungsten, tantalum is collaborative with tungsten and hafnium all can carry further
The stainless intensity of high austenite and resistance to elevated temperatures.
Detailed description of the invention
Detailed description of the invention is set forth below technical scheme is described in further detail.
Embodiment 1
The present embodiment one ultra-low carbon austenitic stainless steel, by mass percentage, its chemical analysis includes: carbon
0.017%, nitrogen 0.2%, manganese 1.75%, chromium 19.4%, nickel 10.6%, silicon 0.39%, aluminum 1.62%, tantalum 2.01%, vanadium
0.64%, hafnium 2.13%, titanium 0.69%, cobalt 0.28%, tungsten 3.04%, molybdenum 1.86%, selenium 0.61%, surplus is ferrum.
Embodiment 2～5
By mass percentage, the chemical analysis of the ultra-low carbon austenitic stainless steel of embodiment 2～5 is as shown in table 1.
The chemical analysis table of the ultra-low carbon austenitic stainless steel of table 1 embodiment 2～5
Comparative example 1～17
By mass percentage, in comparative example 1～19 chemical analysis of austenitic stainless steel as shown in table 2 and table 3.
The chemical analysis table of austenitic stainless steel in table 2 comparative example 1～9
The chemical analysis table of austenitic stainless steel in table 3 comparative example 10～19
Embodiment 6
Be utilized respectively embodiment 1～5 and the austenitic stainless steel material of comparative example 1～19 prepare corrosion-resistant seamless stainless steel
Pipe, comprises the following steps:
(1) just refine
1.: by the mass percent preset, manganese, nickel, chromium, molybdenum, selenium, aluminum and ferrum are placed in electric furnace or converter, 1350
～at 1420 DEG C, carry out melting, the most melted to all the components, it is thus achieved that melting liquid A；
2.: by the mass percent preset, tantalum, hafnium, tungsten, titanium, vanadium and cobalt are placed in electric furnace or converter, 1480～
Melting is carried out at 1620 DEG C, the most melted to all the components, it is thus achieved that melting liquid B；
3.: melting liquid B is warming up to 1550-1750 DEG C, and by preset mass percent, in melting liquid B add carbon,
Nitrogen and silicon, continue melting 3～4h, it is thus achieved that melting liquid C；
4.: melting liquid A is joined in the melting liquid C of 1550-1750 DEG C, be heated to 1650～1850 DEG C, insulation 30～
60min, it is thus achieved that just refine liquid.
(2) refine
It is placed in just refining liquid in AOD furnace, at 1800～1950 DEG C, carries out refine, be incubated 2～2.5h, it is thus achieved that refining liquid,
Acquisition refining liquid is molded intoSteel billet.
(3) electroslag remelting
With argon shield electroslag refining furnace, steel billet is carried out electroslag remelting, after remelting, quickly cool down acquisition's
Ingot casting.
(4) homogenizing anneal
First stage: described ingot casting is heated to 1150～1200 DEG C, it is incubated 10～13h；
Second stage: from 1150～1200 DEG C, annealing temperature is warming up to 1300～1350 DEG C, is incubated 8～11h；
Phase III: annealing temperature is down to 1250～1280 DEG C from 1300～1350 DEG C, it is incubated 10～12h；
Fourth stage: from 1250～1280 DEG C, annealing temperature is down to 1150～1200 DEG C, is incubated 4～6h.
(5) forging
Ingot casting after homogenizing anneal is heated to 1100-1250 DEG C, is incubated 60min, ingot casting is carried out multi-pass forging
Make, make forging stock.
(6) tubulation base
Strip off the skin centering and perforation process to forging stock, makesPipe.
(7) hot extrusion
1.: pipe is placed in annular furnace preheating, annular furnace temperature is set to 1050～1100 DEG C, and the time in stove is
672min (i.e. 1.4 × 480)；
2.: being placed in induction furnace by the pipe after preheating and once heat, induction furnace temperature is 1150～1180 DEG C, protects
Temperature 3min；
3.: once after heating, utilize 1100～1250 DEG C of molten glass powder that the surfaces externally and internally of pipe is lubricated；
4.: after lubrication, use rose bit that pipe is carried out expanding process；
5.: after expanding, being placed in induction furnace by pipe and carry out post bake, induction furnace temperature is 1230～1260 DEG C, protects
Temperature 4min；
6.: after post bake, pipe is squeezed into seamless tube blank, air cooling, it is thus achieved that seamless tube blank external diameter be 324mm, wall
Thick 20.4mm.
(8) solution treatment
Seamless tube blank is heated to 1050～1150 DEG C, after insulation 20min, water-cooled, aligning, pickling, reconditioning, lubrication.
(9) cold deformation processes
Seamless tube blank after solution treatment is carried out cold deformation process, make the contraction percentage of area control 20～40% it
Between, it is thus achieved that gapless stainless steel tube semi-finished product；
(10) stress relief annealing
At 600～800 DEG C, seamless steel pipe semi-finished product are carried out stress relief annealing, it is thus achieved that corrosion-resistant gapless stainless steel tube becomes
Product.
(11) Non-Destructive Testing
By ASME E213 " metal nominal pipe and the practical code of pipe ultrasonic inspection " to obtain corrosion-resistant seamless not
Rust steel pipe finished product carries out ultrasonic examination, and II grade qualified.
(12) tube end maching
Seamless steel pipe finished product qualified for Non-Destructive Testing is cut into the length of needs.
Test case
1, measuring mechanical property
(1) wearability test
By use embodiment 1～5 and the seamless steel pipe for preparing of the austenitic stainless steel material of comparative example 1～13 respectively
Carrying out wearability experiment on MLD-10 type impact abrasive wear testing machine, detailed process is as follows: cut into by seamless steel pipe
The sample of 10mm × 10mm × 30mm, abrasive material is the purity quartzite of 1mm～2mm, and flow is 450mL/min, and ballistic work is
5.0J；Quality after 30min measures once abrasion, measures 5 times altogether, and wear and tear 2h, judges wearability with sample weightlessness；Survey
Test result is shown in Table 4.
(2) hardness, impact flexibility, elongation percentage, tensile strength and yield strength test
Test result is shown in Table 4 and table 5.
The measuring mechanical property result (under room temperature) of each seamless steel pipe of table 4
From table 4, the seamless steel pipe using the ultra-low carbon austenitic stainless steel of embodiment 1～5 to prepare is respectively provided with excellent
Wearability, hardness, impact flexibility, elongation percentage, tensile strength and yield strength.
Compared with Example 1, comparative example 1 is high due to carbon content, and its wearability, hardness and tensile strength are the highest, but punching
Hit toughness, elongation percentage and yield strength to have declined.
Compared with Example 1, the disappearance of silicon in comparative example 2, to the wearability of seamless steel pipe, hardness, impact flexibility, extension
The impact of rate, tensile strength and yield strength is less.
Compared with Example 1, comparative example 3 is due to disappearance aluminum, the wearability of seamless steel pipe, hardness, impact flexibility, extension
Rate, tensile strength and yield strength all decrease, and wherein, wearability and the hardness of seamless steel pipe decline by a big margin, and show
Aluminum has certain effect to the intensity improving ultra-low carbon austenitic stainless steel of the present invention.
Compared with Example 1, comparative example 4 is owing to disappearance tantalum, comparative example 5 are due to disappearance vanadium, the wearability of seamless steel pipe, hard
Degree, impact flexibility, elongation percentage, tensile strength and yield strength are all greatly reduced；And comparative example 6 is owing to lacking tantalum and vanadium simultaneously,
The wearability of seamless steel pipe, hardness, impact flexibility, elongation percentage, tensile strength and yield strength reduce further；Wherein, impact
Declining by a big margin of toughness, elongation percentage and yield strength.Show that tantalum and vanadium all can be effectively improved Ultra-low carbon Ovshinsky of the present invention
The stainless hardness of body, intensity and wearability, and make ultra-low carbon austenitic stainless steel of the present invention be rich in high ductibility and toughness, two
Person Use Limitation fruit simultaneously is more preferably.
Compared with Example 1, comparative example 7 is due to disappearance hafnium, and comparative example 9 is due to disappearance titanium, the wearability of seamless steel pipe, hard
Degree, impact flexibility, elongation percentage, tensile strength and yield strength are all greatly reduced；Comparative example 8 is owing to lacking hafnium and tantalum, right simultaneously
Ratio 10 owing to lacking hafnium and titanium simultaneously, the wearability of seamless steel pipe, hardness, impact flexibility, elongation percentage, tensile strength and surrender
Intensity reduces further；Wherein the declining by a big margin of wearability, hardness and tensile strength；Show that hafnium and titanium all can effectively change
Hardness, intensity and the wearability of rare book invention ultra-low carbon austenitic stainless steel, both use simultaneously or are combined with tantalum (or vanadium)
Time better.
Compared with Example 1, comparative example 11 is due to disappearance tungsten, the wearability of seamless steel pipe, hardness, impact flexibility, extension
Rate, tensile strength and yield strength all decrease；Comparative example 12 owing to lacking tungsten and cobalt simultaneously, the wearability of seamless steel pipe,
Hardness, impact flexibility, elongation percentage, tensile strength and yield strength reduce further, wherein wearability, hardness and tensile strength
Decline by a big margin.This is because tungsten can form tungsten carbide with carbon, tungsten carbide can improve the hard of austenitic stainless steel further
Degree, wearability and resistance to elevated temperatures；And cobalt is not only austenite former, moreover it is possible to work in coordination with tungsten carbide and improve Ovshinsky further
The stainless intensity of body.
Compared with Example 1, comparative example 13 owing to lacking hafnium and tungsten simultaneously, comparative example 14 owing to lacking tantalum and tungsten simultaneously,
Comparative example 15 is owing to lacking tantalum, hafnium and tungsten simultaneously, and comparative example 16 is owing to lacking vanadium, hafnium and tungsten simultaneously, and comparative example 17 is due to simultaneously
Disappearance tantalum, titanium, hafnium and tungsten, the wearability of seamless steel pipe, hardness, impact flexibility, elongation percentage, tensile strength and yield strength enter one
Step reduces.Show between hafnium and tungsten, between tantalum and tungsten, between tantalum, hafnium and tungsten, between vanadium, hafnium and tungsten, between tantalum, titanium, hafnium and tungsten
All there is synergism, it is possible to be effectively improved the hardness of ultra-low carbon austenitic stainless steel of the present invention, intensity and wearability, and make this
Invention ultra-low carbon austenitic stainless steel is rich in high ductibility and toughness.
The measuring mechanical property result (at 600 DEG C/800 DEG C) of each seamless steel pipe of table 5
From table 5, raising with temperature, the impact flexibility of each stainless steel tube, elongation percentage, tensile strength and yield strength are equal
Decline, but when hafnium disappearance (comparative example 7), titanium lacking (comparative example 9), tungsten disappearance (comparative example 11), the impact of stainless steel tube
Declining by a big margin of toughness, elongation percentage, tensile strength and yield strength, and tantalum hafnium lacks (comparative example 8), hafnium and titanium simultaneously
Lacking (comparative example 10), tungsten and cobalt lack (comparative example 12) simultaneously simultaneously, and it is same that hafnium and tungsten lack (comparative example 13), tantalum and tungsten simultaneously
Time disappearance (comparative example 14), tantalum, hafnium and tungsten lacks (comparative example 15) simultaneously, and vanadium, hafnium and tungsten lack (comparative example 16) simultaneously, tantalum,
When titanium, hafnium and tungsten lack (comparative example 17) simultaneously, the impact flexibility of stainless steel tube, elongation percentage, tensile strength and yield strength
Fall is bigger, shows that hafnium, titanium and tungsten are all conducive to improving the resistance to elevated temperatures of stainless steel tube, and tantalum and the addition of cobalt, with
And it is combined, between each alloying element, the resistance to elevated temperatures that all can improve stainless steel tube further.
2, chemical property test
By use embodiment 1～5 and the seamless steel pipe prepared of the austenitic stainless steel material of comparative example 1～13 be respectively placed in
In following corrosive solution:
A, mass fraction are the salpeter solution of 35%；
B, mass fraction are the hydrochloric acid solution of 26%；
C, mass fraction are the sulfuric acid solution of 65%；
D, mass fraction are the bromine water of 2.7%；
E, mass fraction are the formic acid of 5%；
At room temperature and 100 DEG C, corrode 72h respectively, detect each corrosive solution extent of corrosion to each seamless steel pipe, inspection
Survey the results are shown in Table 6.
The decay resistance test result of each seamless steel pipe of table 6
From table 6, use seamless steel pipe prepared by the ultra-low carbon austenitic stainless steel of embodiment 1～5, molten to each corrosion
Liquid is respectively provided with excellent decay resistance, and in comparative example 1, carbon content increases the decay resistance to seamless steel pipe substantially without shadow
Ring.
Comparative example 2 is due to disappearance silicon so that the corrosion resistance of 35% nitric acid has been weakened by seamless steel pipe, rotten to other
The corrosion resistance of erosion solution is then the most suitable with embodiment 5.
Compared with Example 1, after comparative example 3 lacks aluminum, the corrosion resistance of each etchant solution has been dropped by seamless steel pipe
Low, but still the most suitable with embodiment 5.
After comparative example 4 lacks tantalum, the corrosion resistance of each etchant solution is all greatly reduced by seamless steel pipe, and comparative example 5 lacks
After vanadium, the corrosion resistance of each etchant solution is all greatly reduced by seamless steel pipe, and comparative example 6 lacks seamless steel after tantalum and vanadium simultaneously
The corrosion resistance of each etchant solution is reduced by pipe further.Show tantalum and the vanadium decay resistance to improving austenitic stainless steel
There is important function, and when both use simultaneously, the lifting degree of austenitic stainless steel decay resistance is higher.
But during hafnium disappearance (comparative example 7), titanium lacking (comparative example 9), the seamless steel pipe corrosion resistance to each etchant solution
All being greatly reduced, and tantalum hafnium lacks (comparative example 8) simultaneously, hafnium and titanium lack (comparative example 10) simultaneously, and hafnium and tungsten lack simultaneously
(comparative example 13), tantalum and tungsten lacks (comparative example 14) simultaneously, and tantalum, hafnium and tungsten lack (comparative example 15) simultaneously, and vanadium, hafnium and tungsten are simultaneously
Disappearance (comparative example 16), when tantalum, titanium, hafnium and tungsten lack (comparative example 17) simultaneously, seamless steel pipe is corrosion-resistant to each etchant solution
Ability reduces further, shows that tantalum, hafnium, titanium and vanadium are all conducive to improving the decay resistance of stainless steel tube, and each alloying element
Between be combined the decay resistance that all can improve stainless steel tube further.
It is (right that tungsten disappearance (comparative example 11), tungsten and cobalt lack (comparative example 12), molybdenum disappearance (comparative example 18), selenium disappearance simultaneously
Ratio 19) after, the corrosion resistance of each etchant solution is also decreased by rear seamless steel pipe.
Claims (10)
1. a ultra-low carbon austenitic stainless steel, it is characterised in that by mass percentage, its chemical analysis includes: carbon≤
0.02%, nitrogen 0.1～0.25%, manganese 1.6～1.8%, chromium 18～20%, nickel 9～11%, silicon 0.3～0.5%, aluminum 1.5～
1.7%, tantalum 1.5～2.3%, vanadium 0.3～0.8%, hafnium 1.2～2.6%, titanium 0.5～0.8%, cobalt 0.2～0.4%, tungsten 1.6
～3.4%, molybdenum 1～3%, selenium 0.4～0.7%, surplus is ferrum.
2. ultra-low carbon austenitic stainless steel as claimed in claim 1, it is characterised in that by mass percentage, its chemistry becomes
Part includes: carbon≤0.02%, nitrogen 0.18～0.22%, manganese 1.72～1.78%, chromium 18.6～19.7%, nickel 9.4～10.8%,
Silicon 0.36～0.42%, aluminum 1.58～1.65%, tantalum 1.87～2.16%, vanadium 0.54～0.69%, hafnium 1.83～2.24%, titanium
0.66～0.73%, cobalt 0.26～0.32%, tungsten 2.87～3.19%, molybdenum 1.62～2.05%, selenium 0.58～0.64%, surplus
For ferrum.
3. ultra-low carbon austenitic stainless steel as claimed in claim 1, it is characterised in that by mass percentage, its chemistry becomes
Part includes: carbon 0.017%, nitrogen 0.2%, manganese 1.75%, chromium 19.4%, nickel 10.6%, silicon 0.39%, aluminum 1.62%, tantalum
2.01%, vanadium 0.64%, hafnium 2.13%, titanium 0.69%, cobalt 0.28%, tungsten 3.04%, molybdenum 1.86%, selenium 0.61%, surplus is
Ferrum.
4. a corrosion-resistant gapless stainless steel tube, it is characterised in that use the Ultra-low carbon as described in claims 1 to 3 is arbitrary difficult to understand
Family name's body rustless steel is prepared from.
The preparation method of corrosion-resistant gapless stainless steel tube the most as claimed in claim 4, it is characterised in that comprise the following steps:
S1: each raw material of arbitrary for claims 1 to 3 described ultra-low carbon austenitic stainless steel is placed in electric furnace or converter and carries out
Just carry out refine after refining, by acquisition refining liquid continuous casting or be molded into steel billet；
S2: under argon atmosphere, selects ingot shape that described steel billet is carried out electroslag remelting, and after remelting, quickly cooling obtains casting
Ingot；
S3: described ingot casting is carried out homogenizing anneal；
S4: the ingot casting after homogenizing anneal is heated to 1100-1250 DEG C, is incubated more than 30min, ingot casting is carried out multi-pass
Forging, makes forging stock；
S5: strip off the skin centering and perforation process to described forging stock, makes pipe；
S6: described pipe is carried out hot extrusion, makes seamless tube blank；
S7: described seamless tube blank is carried out solution treatment；
S8: the seamless tube blank after solution treatment is carried out cold deformation process, makes the contraction percentage of area control between 20～40%,
Obtain gapless stainless steel tube semi-finished product；
S9: described seamless pipe semi-finished product are carried out stress relief annealing, the described corrosion-resistant seamless stainless steel of the most qualified rear acquisition
Pipe finished product.
6. preparation method as claimed in claim 5, it is characterised in that in step S1, described just refining includes:
S1-1: by the mass percent preset, manganese, nickel, chromium, molybdenum, selenium, aluminum and ferrum are placed in electric furnace or converter, at 1350-
Melting is carried out at 1420 DEG C, the most melted to all the components, it is thus achieved that melting liquid A；
S1-2: by the mass percent preset, tantalum, hafnium, titanium, tungsten, vanadium and cobalt are placed in electric furnace or converter, 1480～1620
Melting is carried out at DEG C, the most melted to all the components, it is thus achieved that melting liquid B；
S1-3: melting liquid B is warming up to 1550-1750 DEG C, and by the mass percent preset, in melting liquid B, add carbon, nitrogen
And silicon, continue melting 3～4h, it is thus achieved that melting liquid C；
S1-4: melting liquid A is joined in the melting liquid C of 1550-1750 DEG C, be heated to 1650～1850 DEG C, insulation 30～
60min, it is thus achieved that just refine liquid.
7. preparation method as claimed in claim 5, it is characterised in that in step S1, described refine includes: just refine liquid by described
It is placed in AOD furnace, at 1800～1950 DEG C, carries out refine, be incubated 2～2.5h, it is thus achieved that described refining liquid.
8. preparation method as claimed in claim 5, it is characterised in that in step S3, described homogenizing anneal includes following rank
Section:
First stage: described ingot casting is heated to 1150～1200 DEG C, it is incubated 10～13h；
Second stage: from 1150～1200 DEG C, annealing temperature is warming up to 1300～1350 DEG C, is incubated 8～11h；
Phase III: annealing temperature is down to 1250～1280 DEG C from 1300～1350 DEG C, it is incubated 10～12h；
Fourth stage: from 1250～1280 DEG C, annealing temperature is down to 1150～1200 DEG C, is incubated 4～6h.
9. preparation method as claimed in claim 5, it is characterised in that in step S6, described hot extrusion comprises the following steps:
S6-1: described pipe is placed in annular furnace preheating, and annular furnace temperature is set to 1050～1100 DEG C, the time in stove is
1.4d min, wherein d is the wall thickness of described pipe；
S6-2: being placed in induction furnace by the pipe after preheating and once heat, induction furnace temperature is 1150～1180 DEG C, insulation
2～4min；
S6-3: once after heating, utilize glass dust that the surfaces externally and internally of pipe is lubricated；
S6-4: after lubrication, carries out expanding process to pipe；
S6-5: after expanding, is placed in pipe in induction furnace and carries out post bake, and induction furnace temperature is 1230～1260 DEG C, is incubated 2
～5min；
S6-6: after post bake, is squeezed into seamless tube blank, air cooling by pipe.
10. preparation method as claimed in claim 5, it is characterised in that in step S7, described solution treatment is: by described nothing
Slit-tube base is heated to 1050～1150 DEG C, water-cooled after insulation 10～30min.
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