CN103014526A - Martensitic stainless steel for valve and manufacturing method thereof - Google Patents
Martensitic stainless steel for valve and manufacturing method thereof Download PDFInfo
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- CN103014526A CN103014526A CN2011102967805A CN201110296780A CN103014526A CN 103014526 A CN103014526 A CN 103014526A CN 2011102967805 A CN2011102967805 A CN 2011102967805A CN 201110296780 A CN201110296780 A CN 201110296780A CN 103014526 A CN103014526 A CN 103014526A
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Abstract
The invention relates to artensitic stainless steel for a valve, comprising the following chemical elements by weight percent: 0.10-0.15 of carbon, 0-0.5% of silicon, 0.5-1.0% of manganese, 0.25-0.50% of nickel, 10.00-13.00% of chromium, 0.01-0.5% of molybdenum, Cu less than or equal to 0.20%, sulphur less than or equal to 0.03%, phosphorus less than or equal to 0.03%, 0.01-0.20% of nitrogen, hydrogen less than or equal to 0.00016%, oxygen less than or equal to 0.0035%, 0.01-0.10% of rare earth, and the balance of Fe and other inevitable impurities. The manufacturing method of the artensitic stainless steel includes the steps of firstly, performing primary melting by an electric arc furnace (EAF), argon oxygen decarburization (AOD)/refining by a ladle furnace (LF), vacuum degassing (VD) and mold casting; secondly, carrying out high-speed forging and cogging, radial forging and hot forging to reach specifications of finished products; and thirdly, performing diffusion hydrogen annealing on forged rods. The obtained martensitic stainless steel has tensile strength of 715-800MPa, yield strength of 570-650MPa, percentage reduction of area of 69-80% and impact toughness (AKv) of 33-83J at minus 29 DEG C.
Description
Technical field
The present invention relates to a kind of Martensite Stainless Steel, particularly relate to a kind of economical oil field valve body with Martensite Stainless Steel and manufacture method thereof, especially relate to the oil field valve body with Martensite Stainless Steel and the manufacture method thereof of large specification, high tenacity, corrosion-resistant steel.
Background technology
The oil field gate valve be flashboard under the drive of valve rod, do relative movement and reach the valve that opens and closes purpose along sealing surface of seat.In recent years, along with the develop rapidly of World Oil Industry, wellhead sluice valve has also obtained rapidly development as the important device in the petroleum drilling and mining equipment, and petroleum industry is also had higher requirement with steel to the oil field valve body.By the requirement of API (API) standard, design temperature is lower than-29 ℃, and (all carbon steel and low alloy steel valve pressure-containing members 20F) should carry out the V-notch pendulum impact test by ISO 148 or ASTM A370.(low-temperature impact 20F) is tested, and ballistic work (AKv) must reach more than the 27J and the part Foreign User requires that the internals of valve body material are carried out-29 ℃ with 13% chromium steel.
Press material and divide, valve body material generally comprises cast iron, structure iron, stainless steel, aluminium alloy, copper alloy, nickel-base alloy, titanium alloy, plastics and pottery etc.Corrosion resistant stainless steel is comparatively widely valve body steel of present purposes.
At present, the oil field valve body mainly is divided into two classes with stainless steel: (1) Chromium Stainless Steel (Ni content is less than 5%), (2) nickel and stainless steel (Ni content is large or equal 5%).
(1) Chromium Stainless Steel (typical steel grade be 410,420,431 etc.), such material manufacturing cost lower (low Ni or do not contain Ni) can satisfy common oil field operation needs; But its low-temperature impact toughness is relatively poor (to exist the shortcomings such as temperature-room type plasticity is poor, temper resistance is poor.540-580 ℃ temper brittleness very easily occurs in this steel grade, it is characterized in that embrittlement of grain boundaries.), only be 15-20J (wherein ,-29 ℃ of impact AKv of 410 only are 10-15J, and-29 ℃ of impact AKv of 431 only are 15-20J), can not satisfy the needs of low temperature petroleum operation.
(2) nickel and stainless steel (typical steel grade be 304,316,321 etc.), low-temperature impact be (29 ℃ are impacted AKv and can reach more than the 100J) better, can satisfy the needs of low temperature petroleum operation; But Ni content has increased the cost of steel greatly up to 5.0%-20.0% (Ni is precious metal element) in the steel, has suppressed the popularization and application of such material.
CN1138880A discloses has good welds and corrosion proof Martensite Stainless Steel and manufacture method thereof, its chemical ingredients is C:0.005-0.035%, below the Si:0.50%, Mn:0.1-1.0%, below the P:0.03%, below the S:0.005%, Mo:1.0-3.0%, Cu:1.0-4.0%, Ni:1.5-5.0%, below the Al:0.06%, below the N:0.01%, and the Cr that satisfies 13＞Cr+1.6Mo 〉=8, and C+N≤0.03,40C+34N+Ni+0.3Cu-1.1Cr 〉=～10, perhaps further also contain Ti:0.05-0.1%, Zr:0.01-0.2%, Ca:0.001-0.02%, among the REM:0.003-0.4% more than one, surplus are Fe basically, present tempered martensite.This steel requires low-carbon (LC), nickelic, high molybdenum, add in addition copper, so cost is higher.
CN1159213A discloses the Martensite Stainless Steel with excellent hot workability and sulfide stress cracking resistance, and its chemical ingredients is C:0.005-0.05%, Si≤0.5%, Mn:0.1-1.0%, P≤0.03%, S≤0.005%, Mo:1.0-3.0%, Cu:1.0-4.0%, Ni:5-8%, and Al≤0.06%, Cr and Mo satisfy the condition of Cr+1.6Mo 〉=13, the element that also randomly contains at least a Ti of being selected from, Zr, Ca and REM, and the Fe of balanced contents.This steel requires low-carbon (LC), nickelic, high molybdenum, add in addition copper, so cost is higher.
In sum, design the oil field valve body Martensite Stainless Steel of the high-performance (29 ℃ are impacted AKv greater than 27J) of a kind of economical (low cost), satisfying the low temperature oil and adopt brill job requirements (authentication requesting of U.S. API standard :-29 ℃ are impacted AKv greater than 27J), is the technology pursue of steelmaker.
Summary of the invention
The object of the present invention is to provide a kind of Eco-power high tenacity oil field valve body Martensite Stainless Steel.
For achieving the above object, economical high tenacity of the present invention oil field valve body Martensite Stainless Steel, its chemical element composition (% by weight) is: carbon: 0.10-0.15%, silicon: 0-0.5%, manganese: 0.5-1.0%, nickel: 0.25-0.50%, chromium: 10.00-13.00%, molybdenum: 0.01-0.5%, Cu≤0.20%, sulphur≤0.03%, phosphorus≤0.03%, nitrogen: 0.01-0.20%, hydrogen≤0.00016%, oxygen≤0.0035%, rare earth: 0.01-0.10%, remaining is Fe and inevitable impurity.
Preferably, rare earth is one or both in cerium and the lanthanum.
Preferably, carbon: 0.12-0.15%.
Preferably, silicon: 0.20-0.45%.
Preferably, manganese: 0.5-0.8%.
Preferably, nickel: 0.25-0.42%.
Preferably, sulphur≤0.01%.
Preferably, chromium: 11-12.5%.
Preferably, molybdenum: 0.02-0.45%, more preferably 0.025-0.35%.
Preferably, copper: 0.05-0.1%.
Preferably, nitrogen: 0.014-0.10%, more preferably 0.015-0.06%.
Preferably, hydrogen≤0.00015%.
Preferably, oxygen≤0.0032%.
Among the present invention, unless otherwise, content all refers to weight percent content.
Above-mentioned economical high tenacity of the present invention oil field valve body Martensite Stainless Steel, its tensile strength is 715-800MPa, and yield strength is 570-650MPa, and relative reduction in area is 69-80%, and-29 ℃ of impact values are 33-83J.
Another object of the present invention is to provide the manufacture method of above-mentioned economical high tenacity oil field valve body Martensite Stainless Steel, and the method comprises:
The first step, electric arc furnace EAF just refines → and AOD/LF refining → VD is degassed → die casting; Second step is forged soon cogging → footpath and is forged forge hot to trimmed size; In the 3rd step, forge rod and expand hydrogen annealing.
Preferably, the first step is to carry out molten steel just to refine in electric arc furnace; The ladle refining of corresponding tonnage; Vacuum outgas; The die casting cast; Produce die casting side's ingot; Steel ingot heat is sent forging.
Preferably; add alloy in liquid steel temperature 〉=1680 ℃ when (preferred 1680-1690 ℃); oxygen decarburization is during to 0.20-0.30%; add lime; end point carbon control 〉=0.08%, the weak stirring and washing of use argon gas before the bull ladle 〉=10 minutes, bull ladle temperature: 1555-1565 ℃; casting process Ar gas protection cast, steel ingot heat in 2 hours is delivered to forge furnace.
Preferably, in the second step, steel ingot heat is delivered to fast forging machine and is carried out cogging, presses the cogging of finished product specification to forging personal base; The integration of operation forging rolling is forged to trimmed size in the footpath; Hot charging annealing.
Preferably, Heating Steel Ingots technique: soaking temperature 1170-1190 ℃, the heat tracing time is not less than 4 hours (preferred 4-5 hour), open the forging temperature and be not less than 1050 ℃ (preferred 1050-1100 ℃), forge personal base and melt down the heat tracing time greater than 3 hours (preferred 3-4 hour).
Final forging temperature is not less than 850 ℃, the type of cooling: hot charging annealing furnace cooling.
Immediately hot charging annealing after rod iron is forged and finished, preferably, hot charging annealing in 30 minutes after rod iron is forged and finished.
Preferably, in the 3rd step, hot charging expands hydrogen annealing after forging excellent finish-forging, Control for Kiln Temperature is waited to expect at 500-600 ℃, forge and be warmed up to 690-710 ℃ per hour to be not more than 80 ℃ speed after rod advances stove, insulation is (preferred 15-20 hour) more than 15 hours, and then (preferred 30-50 ℃/h) cool to 150-200 ℃, insulation is (preferred 4-6 hour) more than 4 hours per hour to be not more than 50 ℃ speed.Then carry out second annealing, (preferred 50-80 ℃/h) speed is warmed up to 670-690 ℃ to be not more than per hour 80 ℃, insulation is more than 15 hours (preferred 15-20 hour), and then (preferred 20-30 ℃/h) speed cools to the 150-250 ℃ of air cooling of coming out of the stove to be not more than per hour 30 ℃.
Forge rod and expand the technology that the hydrogen annealing technology controlling and process is original creation, employing second stage annealing mode has effectively guaranteed the diffusion of hydrogen and has forged the tissue of rod, performance evenly and surface quality, avoided the generation of stress cracking.
Economical valve body of the present invention has reduced nickel content with Martensite Stainless Steel, and cost of alloy is reduced, and has effectively saved nickel resources.Compare with 431 (1Cr17Ni2) Martensite Stainless Steel, nickel has descended 2 percentage points.
The rational chemical ingredients proportioning of steel of the present invention, advanced person's manufacturing process is so that the over-all properties of steel is good.Stainless forging rod of the present invention, after modifier treatment, with conventional Cr-13 type martensitic phase ratio, tensile strength is brought up to 715-800MPa from 540-700MPa, yield strength is brought up to 570-650MPa from 345-550MPa, relative reduction in area is brought up to 69-80% from 55-70%, the raising of large (about 20%) is arranged, and-29 ℃ of impact toughness value (33-83J is than 15-20J) has improved nearly 2 times.
The rational proportion of the elements such as chromium, nickel, molybdenum, nitrogen in the steel of the present invention, so that the corrosion resisting property of steel of the present invention in carbonated and hydrogen sulfide medium improves a lot, simultaneously effective control of the harmful elements such as hydrogen, oxygen has improved corrosion resistance and the welding property of steel.
The chemical ingredients of steel of the present invention reasonable in design.Both guaranteed that its cost was lower, guaranteed again that its hot and cold processing characteristics was not less than existing Cr-13 and Cr-17 type Martensite Stainless Steel.Add simultaneously rare earth at joint nickel and come guaranteed performance with raising nitrogen, manganese content, make it that good structure stability and hot and cold processing characteristics be arranged.
Large specification of the present invention oil field valve body axle class Martensite Stainless Steel carries out in the roller bottom type equipment for Heating Processing that two sections of hot chargings expand hydrogen annealing and whole modifier treatment can obtain good comprehensive mechanical performance: yield strength (Rp0.2) reaches 570-650MPa, tensile strength (Rm) reaches 715-800MPa, unit elongation (A) reaches 18-25%, relative reduction in area (Z) reaches 69-80%, and-29 ℃ of impacts (AKv) are up to 33-83J.
The oil field valve body that steel of the present invention is made has good erosion resistance and low-temperature impact-resistant characteristic.
Description of drawings
Fig. 1 is the forging rod annealing process of steel of the present invention, select different two sections expansion hydrogen annealing techniques to warm soaking time according to the difference of forging excellent final finished specification, the internal stress of Martensite Stainless Steel is fully discharged, simultaneously hydrogen fully spreads and makes homogeneous microstructure, improve toughness, reduced the generation of stress cracking.
Fig. 2 is the metallographic structure of steel of the present invention and the tissue contrast of Cr-13 type Martensite Stainless Steel.Wherein, Fig. 2 is not a) for using the conventional 1Cr13 steel matrix tissue of present technique, Fig. 2 b) be the metallographic structure of steel of the present invention (embodiment 1).As seen, the optimization through composition of steel of the present invention and thermal treatment process makes the matrix of steel more careful and even.
Embodiment
Below by comparatively detailed in conjunction with specific embodiments explanation characteristics of the present invention and effect.
For realizing purpose of the present invention, the Composition Control of steel of the present invention is as follows:
Carbon: carbon is the element of stable austenite, carbon forms the carbide solid solution with alloying elements such as Cr, Mn, Mo and strengthen matrix in ferrite in stainless steel simultaneously, intensity and the hardness of steel are increased substantially, but C is too high then unfavorable to toughness and intergranular corrosion, therefore control carbon is 0.10-0.15% among the present invention, be preferably 0.12-0.15%, can obtaining high-intensity guarantee simultaneously good toughness and erosion resistance.
Manganese: manganese is austenite stabilizer element, but the effect of manganese does not lie in the formation austenite, but is that it reduces the critical quenching rate of steel, increases austenitic stability when cooling, suppresses austenitic decomposition.Therefore manganese can increase the hardening capacity of steel strongly, is conducive to adopt aborning Direct Air-Cooled to be quenched and just can obtains martensitic stucture.Simultaneously, Mn also plays the effect of reductor and sweetening agent, but cleaning molten steel, but too high meeting impels coarse grains, and in addition, aspect the corrosion resistance nature that improves steel, the effect of manganese is little, so control manganese is 0.5-1.0% among the present invention, is preferably 0.5-0.8%.
Silicon: silicon is ferrite former, on forming austenite bad impact is arranged, and along with the raising of silicone content, delta ferrite level will increase in austenitic stainless steel, thereby affect the performance of steel.But the silicon solid solution has obvious strengthening effect in ferrite and austenite.Silicon reduces the solubleness of carbon in austenite, impels Carbide Precipitation, improves intensity and hardness.Simultaneously, the avidity of silicon and oxygen is only second to aluminium and titanium, and be better than manganese, chromium, vanadium, good reductive agent and reductor, can improve the density of steel, but too high plasticity and the toughness that will significantly reduce steel of silicon, so control silicon is 0-0.5% among the present invention, be preferably 0.20-0.45%, can guarantee good obdurability and intergranular corrosion resistance performance.
Chromium: chromium is carbide forming element, has promoted the passivation of steel and has made steel keep stablizing the result of passive state.Simultaneously, chromium is again strongly to form and stablize ferritic element, is dissolved in strengthening matrix in the austenite and not reducing toughness, dwindles the austenitic area, postpones Cooling Austenite Transformation, increases the hardening capacity of steel.Intensity and the hardness of steel are obviously improved, and are useful to anti intercrystalline corrosion and resistance of oxidation.Chromium can crystal grain thinning in addition, improves the temper resistance of quenched and tempered steel, and therefore, steel design chromium content of the present invention is 10.00-13.00%, is preferably 11-12.5%.
Nickel: be to form and the element of stable austenite, improve the tissue of high chromium steel, stainless corrosion resistance nature and processing performance are improved, make steel have the cooperation of good intensity and plasticity, toughness.But nickel is the main alloy element that affects the stainless steel cost, and therefore, control nickel content is 0.25-0.50% among the present invention, is preferably 0.25-0.40%.
Molybdenum: molybdenum is to form ferritic element, and molybdenum can improve the mechanical behavior under high temperature of austenitic stainless steel, can also form the Precipitation phase in stainless steel, improves the intensity of steel.In addition, the spot corrosion that the adding of molybdenum can impel the stainless steel surface passivation and the hydrogen atom of effectively drawing up forms in the metallic surface, has the ability that strengthens stainless steel pitting corrosion and crevice corrosion, therefore, control molybdenum content is 0.010-0.50%, be preferably 0.02-0.45%, more preferably 0.025-0.35%.
Copper: copper is austenite former, and copper can be present in steel in the sosoloid to improve hardening capacity and the intensity of steel, also can improve stainless corrosion resistance nature, but can affect plasticity and the impelling strength of steel.Easily cause the hot tearing of steel during copper＞0.2%.Therefore, control the content of copper is 0-0.20%, is preferably 0.05-0.10%.
Nitrogen: being the important element in the stainless steel, is a kind of effective element that improves stainless steel intensity, erosion resistance and stabilization of austenite, except replacing part of nickel to save the valuable nickel element, also can improve intensity and the corrosion resistance nature of steel.Therefore consider that from strong plasticity and cold and hot working performance, fatigue property and high-temperature corrosion resistance performance steel of the present invention adds the nitrogen of 0.01-0.20%, is preferably 0.014-0.10%, more preferably the nitrogen of 0.015-0.06% is for suitable.
Hydrogen: hydrogen is the harmful element in the steel, can cause that hydrogen causes embrittlement and hydrogen causes delayed fracture (hydrogen embrittlement), promotes Room Temperature Creep, even form white point in steel, forms the performance that harm such as welding hydrogen induced cracking affects steel.In addition, hydrogen atom also easily causes the spot corrosion of metallic surface, especially should prevent in petroleum industry.Therefore, the control hydrogen richness is in 0.00016% (1.6ppm), is preferably in 0.00015% more preferably 0.0001%.
Oxygen: oxygen be in the steel harmful element therefore, too much oxygen can be separated out from molten steel when solidification of molten steel, forms inclusion or bubble, thereby seriously reduces mechanical property, especially plasticity and the toughness of steel.In addition, oxygen also can aggravate the red brittleness harm of sulphur.Therefore, the control oxygen level is in 0.0035% (35ppm), is preferably in 0.0032%.
Rare earth: it is effectively improving hot workability in stainless steel, and rare earth has and purifies and metamorphism, can improve inclusion morphology, reduces the carbide segregation, again can crystal grain thinning, therefore can improve plasticity and the toughness of steel.Rare earth also can improve the oxidation-resistance of high temperature steel in addition.The rare earth that adds 0.01-0.10% can function as described above, and is preferably cerium and lanthanum.
Sulphur, phosphorus, lead, antimony, bismuth should reduce its content as far as possible in technical qualification permission situation simultaneously, to reduce the segregation at original austenite crystal prevention place, improve toughness.Residual element and gas content are controlled at suitable low levels level, make steel have quite high purity, reach desirable best proportioning content between carbon and each element, thereby make material have the over-all propertieies such as good intensity, toughness, erosion resistance.
The preparation method of above-mentioned oil field valve body Martensite Stainless Steel, adopt three-step approach production: for example, the first step, electric arc furnace EAF just refines → and AOD/LF refining → VD is degassed → die casting; Second step, forge hot is forged to trimmed size in 4000 tons of fast ton footpaths, cogging → 1300 of forging; In the 3rd step, forge rod and expand hydrogen annealing.
The first step, electric arc furnace just refine → and AOD/LF refining → VD is degassed → die casting
Carrying out molten steel in the electric arc furnace of 20-60 ton just refines; The ladle refining of corresponding tonnage; Vacuum outgas; The die casting cast; Produce the qualified die casting side ingot of 2.3t, 3.7t or 5.9t; Steel ingot heat is sent forging.
Technology point:
Add alloy during liquid steel temperature 〉=1680 ℃ (preferred 1680-1690 ℃); oxygen decarburization is during to 0.20-0.30%; add lime 1000-1200kg; end point carbon control 〉=0.08% (preferred 0.08-0.10%); use the weak stirring and washing of argon gas 〉=10 minutes (preferred 10-20 minute) before the bull ladle; bull ladle temperature: 1555-1565 ℃, casting process Ar gas protection cast, steel ingot (preferred 0.5-2 hour) heat in 2 hours is delivered to forge furnace.
Second step: integration of operation forge hot finished product and annealing are forged in fast footpath
Steel ingot heat is delivered to 4000 tons of fast forging machines and is carried out cogging, presses different cogging to 280 anises of finished product specification, the personal base of 350 forgings anistree or 400 anises; The integration of operation forging rolling is forged to trimmed size in 1300 tons of footpaths; Hot charging annealing.
Technology point:
Heating Steel Ingots technique: 1180 ± 10 ℃ of soaking temperatures, the heat tracing time is not less than 4 hours (preferred 4-5 hour), opens the forging temperature and is not less than 1050 ℃, forges personal base and melts down the heat tracing time greater than 3 hours (preferred 3-4 hour);
Final forging temperature is not less than 850 ℃ (preferred 850-900 ℃), the type of cooling: hot charging annealing furnace cooling;
Immediately (in 30 minutes) hot charging annealing after rod iron is forged and finished.
The 3rd step: finished product expands hydrogen annealing technique:
As shown in Figure 1, hot charging expands hydrogen annealing after forging excellent finish-forging, Control for Kiln Temperature is waited to expect at 550 ± 50 ℃, forging rod advances behind the stove with the speed that is not more than per hour 80 ℃ (preferred 50-80 ℃/hour) to be warmed up to 700 ℃ of (temperature difference be controlled at ± 10 ℃ in) insulations more than 15 hours (preferred 15-20 hour), then (preferred 30-50 ℃/h) speed cools to 150-200 ℃, and insulation is (preferred 4-6 hour) more than 4 hours to be not more than per hour 50 ℃.Then carry out second annealing, be warmed up to 680 ℃ of (temperature difference be controlled at ± 10 ℃ in) insulations more than 15 hours (preferred 15-20 hour) with the speed that is not more than per hour 80 ℃ (preferred 50-80 ℃/hour), then (preferred 20-30 ℃/h) speed cools to 200 ℃ ± 50 air coolings of coming out of the stove to be not more than per hour 30 ℃.
Tissue, the performance even and surface quality of the present invention by adopting the second stage annealing mode effectively to guarantee the diffusion of hydrogen and forging rod avoided the generation of stress cracking.
The finished product quenching-and-tempering process:
Table 1 finished product quenching-and-tempering process
Table 1 finished product quenching-and-tempering process
Embodiment
Embodiment 1
The first step: smelt
40 tons of EAF electric arc furnace just refine, and end stir mode adopts nitrogen, and silicon carbide, silicon ball are used in the electric furnace reduction agent; Just refining turns the refining of 40 tons of AOD/LF stoves after finishing, and draws clearly reducing slag before the tapping, adds alloy, end point carbon 〉=0.08%, vacuum outgas 66.7Pa at least 10 minutes, soft blow argon 10 minutes, 1560 ℃ of bull ladle temperature in the time of 1680 ℃; 2.3 tons of steel ingots of die casting water finishes lifting after 120 minutes, after the steel ingot demoulding in 2 hours heat deliver to forge furnace.
Second step: forge
It is the 280 anistree bases of using by oneself that forge that steel ingot heat is delivered to the cogging of 4000 tons of fast forging machines, melt down and be heated to 1050 ℃ of insulations 1.5 hours and forge rod by 1300 tons of footpath forged pieces, 850 ℃ of finish-forgings, as shown in Figure 1, carry out hot charging annealing, the second stage annealing insulation after 30 hours furnace cooling to 200 ℃ come out of the stove.
The 3rd step: modified
Forge excellent sample modifier treatment, 950 ℃ of insulations oil quenchinng of coming out of the stove after 20 minutes; Be chilled to and advance the stove tempering below 200 ℃, tempering process be 700-720 ℃ of insulation after 1.5 hours water-cooled and 650-680 ℃ insulation after 1.5 hours water-cooled to room temperature.
Composition such as the table 2 of other embodiment, technological process such as embodiment, processing parameter is as shown in table 3.
The chemical ingredients of table 2 embodiment of the invention 1-5 steel and comparative example
| Embodiment | C | Mn | P | S | Si | Cr | Ni | Cu | Mo | Ce+La | N | H | O |
| 1 | 0.14 | 0.56 | 0.016 | 0.001 | 0.38 | 12.03 | 0.26 | 0.06 | 0.04 | 0.01 | 0.030 | 0.0001 | 0.0025 |
| 2 | 0.13 | 0.57 | 0.017 | 0.001 | 0.41 | 11.88 | 0.31 | 0.07 | 0.03 | 0.03 | 0.050 | 0.0001 | 0.0030 |
| 3 | 0.14 | 0.76 | 0.023 | 0.001 | 0.42 | 12.02 | 0.32 | 0.09 | 0.05 | 0.10 | 0.056 | 0.0001 | 0.0016 |
| 4 | 0.14 | 0.59 | 0.017 | 0.004 | 0.20 | 12.10 | 0.38 | 0.06 | 0.19 | 0.03 | 0.030 | 0.0001 | 0.0020 |
| 5 | 0.14 | 0.60 | 0.019 | 0.004 | 0.13 | 11.90 | 0.41 | 0.06 | 0.30 | 0.01 | 0.015 | 0.0001 | 0.0022 |
| 1Cr13 | 0.1 | 0.43 | 0.02 | 0.004 | 0.38 | 12.3 | 0.2 | 0.08 | 0.04 | 0 | 0.020 | 0.0003 | 0.0040 |
The processing parameter of table 3 embodiment of the invention 1-5 steel
Test example 1: mechanical property
According to the mechanical propertys such as tensile strength, yield strength, elongation, relative reduction in area, impelling strength and hardness of GB/T 228 mensuration embodiment of the invention 1-5 steel, its result is as shown in table 4.
The mechanical property of table 4 embodiment of the invention 1-5 steel
Test example 2: metallographic structure
Fig. 2 is the metallographic structure of steel of the present invention and the tissue contrast of Cr-13 type Martensite Stainless Steel.Wherein, Fig. 2 is not a) for using the conventional 1Cr13 steel matrix tissue of present technique, Fig. 2 b) be the metallographic structure of steel of the present invention (embodiment 1).As seen, the optimization through composition of steel of the present invention and thermal treatment process makes the matrix of steel more careful and even.Other embodiment also can obtain same result.
Reach from the above description embodiment as seen, implement the forge hot pole that the present invention produces, room-temperature mechanical property when not reducing intensity index larger raising plasticity index, more make low temperature impact properties apparently higher than 1Cr13,2Cr13 and 1Cr17Ni2, for the working conditions that improves oil field valve body martensitic steel, particularly for solving valve body axle impelling strength low problem in oil field under the low temperature, improve the very important realistic meaning of petroleum operation efficient tool.
Steel of the present invention and the stainless performance comparison of conventional 1Cr13 are as shown in table 5.
Table 5 steel of the present invention and the stainless performance comparison of conventional 1Cr13
From table 5 result as seen, embodiments of the invention 1-5 steel is compared with conventional 1Cr13 Martensite Stainless Steel, and 20 ℃ of impact values have on average improved about 1.5 times, and-29 ℃ of impacts have on average improved nearly 2 times.
The present invention is by optimizing and the strict chemical ingredients of controlling steel, increase Mn, N content, reduce Cr, Ni, Si content and H, O content, and suitably add rare earth element, adopt simultaneously suitable expansion hydrogen annealing technique and hardening and tempering process, stable, the uniform quenched and tempered organization of final acquisition is to improve strong plasticity and the impelling strength of steel; Solved the on the low side and easy problem that stress crack and low-temperature brittle fracture occur of the low-temperature impact toughness of using Martensite Stainless Steel in existing oil field on the basis that does not increase smelting cost.The oil field valve body Martensite Stainless Steel that the present invention produces, low cost of manufacture, the Integrated using performance reaches standard (the tensile strength 655MPa of API 6D, yield strength 520MPa, unit elongation 18%, relative reduction in area 35%, low-temperature impact toughness :-29 ℃ are impacted AKv and will reach more than the 27J) meet Foreign User high standard authentication requesting; Simultaneously, can improve the resistance to overturning of petroleum drilling and mining equipment, further satisfy the requirement of development of oil industry.The present invention is particularly effective for being used on the valve body of low temp operation oil field, has greatly improved operating efficiency, has reduced failure rate and cost for oil production.
Claims (21)
1. Martensite Stainless Steel, the chemical element composition of its weight percent meter is: carbon: 0.10-0.15%, silicon: 0-0.5%, manganese: 0.5-1.0%, nickel: 0.25-0.50%, chromium: 10.00-13.00%, molybdenum: 0.01-0.5%, Cu≤0.20%, sulphur≤0.03%, phosphorus≤0.03%, nitrogen: 0.01-0.20%, hydrogen≤0.00016%, oxygen≤0.0035%, rare earth: 0.01-0.10%, remaining is Fe and inevitable impurity.
2. Martensite Stainless Steel as claimed in claim 1 is characterized in that, rare earth is one or both in cerium and the lanthanum.
3. Martensite Stainless Steel as claimed in claim 1 or 2 is characterized in that, carbon: 0.12-0.15%.
4. such as the arbitrary described Martensite Stainless Steel of claim 1-3, it is characterized in that silicon: 0.20-0.45%.
5. such as the arbitrary described Martensite Stainless Steel of claim 1-4, it is characterized in that manganese: 0.5-0.8%.
6. such as the arbitrary described Martensite Stainless Steel of claim 1-5, it is characterized in that nickel: 0.25-0.42%.
7. such as the arbitrary described Martensite Stainless Steel of claim 1-6, it is characterized in that sulphur≤0.01%.
8. it is characterized in that chromium such as the arbitrary described Martensite Stainless Steel of claim 1-7: 11-12.5%.
9. such as the arbitrary described Martensite Stainless Steel of claim 1-8, it is characterized in that molybdenum: 0.02-0.45%.
10. such as the arbitrary described Martensite Stainless Steel of claim 1-9, it is characterized in that copper: 0.05-0.1%.
11. such as the arbitrary described Martensite Stainless Steel of claim 1-10, it is characterized in that nitrogen: 0.014-0.10%.
12. such as the arbitrary described Martensite Stainless Steel of claim 1-11, it is characterized in that hydrogen≤0.00015%.
13. such as the arbitrary described Martensite Stainless Steel of claim 1-12, it is characterized in that oxygen≤0.0032%.
14. such as the arbitrary described Martensite Stainless Steel of claim 1-13, its tensile strength is 715-800MPa, yield strength is 570-650MPa, and relative reduction in area is 69-80%, and-29 ℃ of impact AKv are 33-83J.
15. the manufacture method such as the arbitrary described Martensite Stainless Steel of claim 1-14 comprises:
The first step, electric arc furnace EAF just refines → AOD/LF refining → VD is degassed → and die casting pours into steel ingot, and steel ingot heat is sent forging; Second step, steel ingot are forged soon cogging → footpath and are forged forge hot to trimmed size; In the 3rd step, forge rod and expand hydrogen annealing.
16. method as claimed in claim 15; it is characterized in that; in the first step, add alloy during in liquid steel temperature 〉=1680 ℃, oxygen decarburization is during to 0.20-0.30%; add lime; end point carbon control 〉=0.08%, the weak stirring and washing of use argon gas before the bull ladle 〉=10 minutes, bull ladle temperature: 1555-1565 ℃; casting process Ar gas protection cast, steel ingot heat in 2 hours is delivered to forge furnace.
17. such as claim 15 or 16 described methods, it is characterized in that, in the first step, add lime 1000-1200kg.
18. such as the arbitrary described method of claim 15-17, it is characterized in that, the soaking temperature of Heating Steel Ingots is 1170-1190 ℃, the heat tracing time is not less than 4 hours, press the different coggings of finished product specification to forging personal base, open the forging temperature and be not less than 1050 ℃, forge personal base and melt down the heat tracing time greater than 3 hours;
Final forging temperature is not less than 850 ℃, the type of cooling: hot charging annealing furnace cooling;
Immediately hot charging annealing after rod iron is forged and finished.
19. method as claimed in claim 18 is characterized in that, rod iron is forged and is finished hot charging annealing in rear 30 minutes.
20. such as the arbitrary described method of claim 15-19, it is characterized in that, forging rod in the 3rd step expands in the hydrogen annealing, Control for Kiln Temperature is waited to expect at 500-600 ℃, forge rod and advance that the speed with≤80 ℃/h is warmed up to 690-710 ℃ behind the stove, insulation is more than 15 hours, then the speed with≤50 ℃/h cools to 150-200 ℃, insulation is more than 4 hours, then carry out second annealing, speed with≤80 ℃/h is warmed up to 670-690 ℃, and then insulation cooled to the 150-250 ℃ of air cooling of coming out of the stove with≤30 ℃ speed more than 15 hours.
21. method as claimed in claim 20, it is characterized in that, forging rod in the 3rd step expands in the hydrogen annealing, Control for Kiln Temperature is waited to expect at 500-600 ℃, forging rod advances behind the stove with 50-80 ℃ speed per hour to be warmed up to 690-710 ℃, be incubated 15-20 hour, then cool to 150-200 ℃ with 30-50 ℃ speed per hour, be incubated 4-6 hour, then carry out second annealing, be warmed up to 670-690 ℃ with 50-80 ℃ speed per hour, be incubated 15-20 hour, then cool to the 150-250 ℃ of air cooling of coming out of the stove with 20-30 ℃ speed per hour.
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| CN103423470A (en) * | 2013-08-29 | 2013-12-04 | 南通捷瑞阀门有限公司 | Manual non-rising stem type gate valve and heat treatment process of valve body thereof |
| CN103451541A (en) * | 2013-08-29 | 2013-12-18 | 钢铁研究总院 | Martensite stainless steel applicable to rotor of shield pump of nuclear power station |
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