CN104630565A - High-strength and high-plasticity Ni-Cr-Co based turbine disc blade material and preparation method thereof - Google Patents
High-strength and high-plasticity Ni-Cr-Co based turbine disc blade material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a turbine disc blade material and a preparation method thereof. The turbine disc blade material comprises the following components in percentage by weight: 15.50-19.50% of Cr, 18.0-21.0% of Co, 2.5-3.4% of Ti, 1.3-2.0% of Al, not larger than 0.15% of Zr, not larger than 0.02% of B, not larger than 1.0% of Mn, 0.05-0.07% of C, not larger than 0.004% of P, not larger than 0.004% of S, not larger than 1.0% of Si, not larger than 2.0% of Fe, not larger than 0.2% of Cu, not larger than 0.015% of impurities and the balance of nickel. The material provided by the invention has good high temperature properties, and can meet the requirements of high strength and high plasticity at room temperature and good machining properties.
Description
Technical field
The present invention relates to Material Field, particularly a kind of high-strength high-plasticity Ni-Cr-Co base turbine dish blade material and preparation method.
Background technology
Modern industry flourish, energy saving standard is brought into schedule gradually.Current petroleum system, in order to increase economic efficiency and adapt to the requirement of Environmental Safety, all adopts flue-gas expander power generation system to carry out UTILIZATION OF VESIDUAL HEAT IN to catalytic cracking unit high-temperature flue gas out.Flue gas turbine expander (calling cigarette machine in the following text) is the important device of the industrial sector cogenerations such as refinery, the key part of the turbine disk, blade cigarette machine especially.
The huge heat that contains in the high-temperature flue gas that refinery oil refining produces, be usually used in generating, cigarette machine is for device for generating power by waste heat, and due to working conditions very severe, and hot conditions also can the failure damage of accelerated material.Containing impurity elements such as a large amount of S, C in flue gas, be easy under the high temperature conditions and 0 in air
2, H
2o etc. react, and generate SO
2, SO
3, H
2the gaseous product that S, CO etc. are harmful.Under hot conditions, corrosive gases flow at high speed, easily causes the oxidation of material, sulfuration and thermal etching, thus reduces the work-ing life of material.Once cigarette machine destroys, the property caused and personal damage are difficult to the appraisal, so should be very careful for the selection of cigarette machine material, for the material of cigarette machine material, require that there is higher intensity and certain toughness, there is high thermotolerance and solidity to corrosion simultaneously.
Along with the progress of science and technology, be used as civilian flue gas turbine expander and Gas Turbine dish and blade in the past, and be difficult to meet current generation development need.At present, domestic flue gas turbine expander turbine disk diameter does larger and larger, and the diskware diameter prepared reaches 1250mm, but the blade matched with it is usually not high due to intensity, and toughness plasticity is bad, and causes leaf destruction.
According to statistics, annual China flue gas turbine expander turbine disk and blade material and the every annual requirement of element at 2000 ~ 3000 tons, and the current lumber recovery of China be only 20% less than, the life and reliability of blade is unstable simultaneously.Cause petroleum chemical industry flue gas turbine expander turbine disk blade to rely on import in a large number, domestic market occupancy volume is very little.
Summary of the invention
Order of the present invention is to provide a kind of high-strength high-plasticity Ni-Cr-Co base turbine dish blade material and preparation method, and described material has good high-temperature behavior, can meet the requirement that room temperature high-strength high-plasticity, machining property are good.
Technical scheme of the present invention is as follows:
The material of high-strength high-plasticity Ni-Cr-Co base turbine dish blade, the weight percent of its each component is: Cr:15.50 ~ 19.50%; Co:18.0 ~ 21.0%; Ti:3.1 ~ 3.4%%; Al:1.3 ~ 2.0%; Zr≤0.15; B≤0.02%; Mn≤1.0%; C:0.05 ~ 0.07%; P≤0.004%; S≤0.004%, Si≤1.0%; Fe≤2.0%; Cu≤0.2%; Impurity≤0.015%; Surplus is nickel.
The good technical scheme of material of the present invention is, the weight percent of each component is: C:0.05 ~ 0.07%, Co:19 ~ 21%, Cr:16 ~ 18%, Ti:3.1 ~ 3.4%, Al:1.3 ~ 1.5%, Zr≤0.08, Mn≤0.20, B≤0.009, P≤0.004%; S≤0.004%, Si≤1.0%; Fe≤2.0%; Cu≤0.2%; Impurity≤0.015%; Surplus is nickel.
Described impurity is Pb, As, Sb, Sn, Zn, Bi.
Another object of the present invention is to provide a kind of preparation method of high-strength high-plasticity Ni-Cr-Co base turbine dish blade material, and it has following steps:
1) by above-mentioned proportion ingredient;
2) step 1) described in batching, vacuum oven 2 refinings at 1530 ~ 1560 DEG C, stir, thread middling speed evenly pours into a mould 12 ~ 18 seconds, obtains resmelting electrode rod;
3) step 2) described in resmelting electrode rod obtain the thermal treatment of alloy pig homogenizing through vacuum consumable remelting, be forged into the bar for turbine disk blade material.
Step 2) first time refining time in described 2 refinings is 10 ~ 20 minutes, vacuum tightness is 1 ~ 0.1Pa; Second time refining time is 10 minutes, vacuum tightness 0.1 ~ 0.002Pa.
Step 3) described vacuum consumable remelting time be filled with helium, when being filled with helium, vacuum tightness≤6.5Pa.
Step 3) described in homogenizing heat-treating methods be holding temperature 1170 DEG C, diameter is greater than the alloy pig of 200mm, and soaking time is every 1mm soaking time is 1.5min; Diameter is less than 200mm alloy pig, and soaking time is 5h.
Step 3) initial forging temperature of described forging is 1180 DEG C, finish-forging >=1000 DEG C.
Step 3) gained bar need forge processing, finishing, and forging adds man-hour, and bar heats up with stove, and the temperature of processing is 1000 ~ 1180 DEG C.
Step 3) described bar specification is diameter of phi 20mm ~ Φ 400mm.
The effect of each element in material of the present invention:
Ni is alloy substrate element, and Main Function is stable austenite tissue, and ensureing the processing characteristics of alloy, is also the basis ensureing good mechanical behavior under high temperature.
Chromium can improve the oxidation-resistance of iron-based and nickel-base high-temperature high elastic modulus alloy, and along with the increase of Cr content, material can obtain higher thermostability, and it can form anti-oxidant and erosion-resisting rich Cr in metallic surface
2o
3protective layer, depends on metallic surface to this protective layer compact and firm, prevents the harmful elements such as O, N, S to the diffusion of material internal, thus significantly improve oxidation-resistance and the high temperature corrosion resistance of alloy.Appropriate chromium can make alloy in medium, have good solidity to corrosion.Appropriate chromium also can improve the solidity to corrosion of alloy in oxidizing acid solution, and when particularly Cr, Ni proportioning is appropriate, solidity to corrosion is more excellent.For obtaining good antioxidant property, in alloy, need the Cr adding 19% ~ 20%.
Co is at room temperature close-packed hexagonal structure, changes face centered cubic austenite structure when being heated to 420 DEG C into.Because austenite spread coefficient is little, a large amount of alloying element of energy solid solution, has higher hot strength, mainly plays solution strengthening effect, can reduce Ti and Al solubleness in the base, thus increase the quantity of strengthening phase; Co can also improve the solid solubility temperature of γ ' phase; Reduce the precipitation of carbide on crystal boundary, to reduce the width of crystal boundary Cr depletion zone; Improve the hot workability of nickel base superalloy, moulding and impelling strength also plays an important role, and corrosion and heat resistant energy force rate nickel is good.In superalloy, the antioxidant property of cobalt is poor, and therefore Co considers design con-trol scope is 17.0 ~ 18.0%.
Al generates fine and close nonvolatile Al at alloy surface
2o
3oxide film, Al
2o
3film compares Cr
2o
3film has better resistance of oxidation and lower rate of oxidation, can overcome the Cr of alloy surface
2o
3film is easily oxidized to volatile CrO during long term operation more than 1200 DEG C
3and the weakness be damaged, make alloy have better high-temperature oxidation resistance, can be used for higher temperature, the molecular motion between the foreign matter that can effectively suppress body under the condition of high temperature to be in contact with it.Add appropriate Al, alloy inner oxidation can be reduced and form fine and close external oxidation protective membrane.The content of this project control Al is 1.3% ~ 1.5%.
Ti, Al are the principal elements of alloy strengthening, play ageing strengthening effect.Ti, Al can interact with the Ni in steel and form Ni3 (TiAl) intermetallic compound, significantly improve the hot strength of alloy.C in Ti and alloy interacts and forms TiC.These second-phases not only stable components, more importantly not easily agglomeration.At high temperature keep certain quantity, size and the γ ' phase of Dispersed precipitate, can remarkable reinforced alloys.But Ti, Al are ferritic phase promotes element, and too high amount can reduce toughness of material greatly, and can worsen materials hot working performance, thus needs conservative control.Therefore Ti design con-trol is 3.1 ~ 3.4%.
B, Zr: add appropriate B, Zr in alloy, be mainly present on crystal boundary, can change Grain boundary morphology.Under high temperature, grain boundary decision is rapid, be the passage that dislocation is easily climbed, and B atom is enriched on crystal boundary, fills up room and other lattice imperfection, reduces climb of dislocation speed, thus reinforced alloys.B on crystal boundary can also suppress gathering in early days of Cr23C6, delays the generation of grain-boundary crack.In addition B also reduces C to grain boundary segregation, increases the quantity of carbide in crystal boundary, thus reinforced alloys.B reduces interfacial energy on crystal boundary, the formation of second-phase on favourable crystal boundary, makes it to be easier to form spheroidal, improves grain-boundary strength.Therefore the B added can significantly improve the creep rupture life of alloy, reduces creep rate, and significantly improves persistent notch sensitivity, put forward heavy alloyed plasticity and processing characteristics.But too high B, crystal boundary is formed hard and crisp compound, or the compound of low melting point, causes plasticity to decline, hot workability is deteriorated.The content of B controls 0.005% ~ 0.01%.
Mn can play the effect of deoxidation, purification alloy in the alloy.But the membership that adds of manganese reduces the lower stainless corrosion resisting property of chromium amount a little.When chrome content in alloy is enough high (17%Cr), the solidity to corrosion of manganese alloy there is no harmful effect.This project Mn design load less than 0.35%.
Si reduces γ phase block elements, and certain silicon can play the effect of deoxidation, purification alloy, but Si content is higher, the fragility of alloy material will be increased, Drawing abillity is reduced, and therefore Si is controlled in this alloy, and the content of this development alloy designs Si controls≤0.20%.
The carbon that affects of C is the strong forming element of austenite, and along with carbon content increases, hardness strength improves, and plasticity reduces.C is the fundamental element forming carbide reinforced phase, but is also the element strongly reducing alloy melting point.For requiring the casting alloy with high creep strength, the control of carbon content is most important.As the alloy used under ultrahigh-temperature, single from the viewpoint of fusing point, too high carbon content is also unsuitable.In this superalloy, strengthen crystal boundary by the formation of various Mc carbide, adding C can reduce oxide compound, puies forward heavy alloyed clarity.The composition of this project control C is 0.06 ~ 0.08%.
Content to be controlled at below 60ppm by vacuum melting and vacuum consumable remelting for harmful elements such as S, P.Within 8ppm is strict controlled in for O.
Ni-Cr-Co base turbine dish blade material of the present invention and Exemplary chemical composition analysis value are in table 1.
Table 1 invention alloy composition wt%
Element | Content (%) |
C | 0.05~0.08 |
Cr | 15.50~19.50 |
Co | 18.0~21.0 |
Ti | 2.5~3.4 |
Al | 1.3~2.0 |
Zr | ≤0.15 |
B | ≤0.02 |
Mn | ≤1.0 |
Si | ≤1.0 |
P | ≤0.006 |
S | ≤0.006 |
Fe | ≤2.00 |
Cu | ≤0.2 |
Impurity | ≤0.015 |
Ni | Surplus |
The span of control of table 2 detrimental impurity element
Compared with conventional turbine disk blade material, the premium properties that alloy bar material of the present invention has, specifically in table 3.
The mechanical property of table 3 material
After testing, the high-temperature behavior of invention material is: 870 DEG C, Rm:200MPa, τ >=100h, A5 >=5%.
Vacuum consumable remelting affects the metallurgical quality of alloy pig greatly, and it is one of critical process of Ni-Cr-Co base turbine dish blade material metallurgical quality control.Vacuum consumable remelting substantially improves ingot crystal state, reduces inclusion content, improves inclusion distribution state, denitrogenates and hydrogen, elimination macroscopic view and microscopic defect, the segregation alleviated in alloy pig.
What time following note in vacuum consumable remelting in technique:
A. smelting temperature is not easily too high, and the too high meeting of temperature causes Mn, C solidifying segregation, and remelting temperature controls in (1530 ~ 1560) ± 5 DEG C;
B., in consumable reflow process, the control of electric current is extremely important, ensure normal smelting disperse arc condition under, the increase of electric current to stably fused process, to change surface quality and improve melting efficiency be favourable.But the growth of electric current has a definite limitation, after current value reaches the limit values, arc behavior will disperse the phenomenon that arc changes to narrow arc, metal drop is caused directly to drive to steel ingot center, affect the exclusion process of inclusion, cause the width of pool depth and two-phase region all to strengthen simultaneously, enhance the segregation tendency of alloy.Certainly too low electric current is equally also disadvantageous to metallurgical quality and production efficiency.In consumable remelting, current control is at 2500 ~ 3000A;
C. the control of helium gas flow, when vacuum consumable, introducing helium between alloy pig ingot and crystallizer is to improve the dynamic conditions solidified, microcosmic is formed nonequilibrium state solidify, alloy pig as-cast structure dendrite is attenuated, low-alloyed segregation tendency, falls in the axial dendrite range widens of parallel alloy pig.Helium gas flow is not easily excessive, and excessive helium makes the vacuum tightness in burner hearth reduce, and destroys arc behavior, affects melting pool shape.When arc behavior fluctuates, sweep from crystallizer wall the splashings fallen and can fall into the molten bath that shape changes, and directly fix by the two-phase region above moved after, form the oxide inclusion of bulk.When being filled with helium, vacuum tightness keeps being not more than 6.5Pa.
High-strength high-plasticity Ni-Cr-Co base turbine dish blade material of the present invention, meet the needs in the fields such as national oil chemical industry, space flight, aviation, compared with existing wasPaloy, GH4738, NCK20TA material, material of the present invention is by the content of adjustment Co, Ti, Al, control the content of strengthening phase, make material composition completely different from similar products at home and abroad with weave construction.The high strength that has invention material has both better plasticity, high impact resistance, superior machining property.High-strength high-plasticity Ni-Cr-Co base turbine dish blade material of the present invention, by to material chemical composition design, purity, clean smelting technology, processing and thermal treatment process, and vacuum melting technique, reduce O, S, P content, improve inclusion morphology, gained is used for turbine disk blade material and has good intensity, high impact properties, excellent fatigue lifetime, high-ductility.Vacuum melting electrode bar of the present invention, again by vacuum consumable remelting processing, manufactures all size bar needed for turbine disk blade processing.Material solid solution+aging state room-temperature mechanical property of the present invention: Rm >=1140MPa, Rp0.2 >=785MPa, A >=20%, Z >=30%; Solid solution state HB≤302, HV5≤340; 870 DEG C, Rm:200MPa, τ >=30h, A (5D or 50mm) >=3.5%.
Specific embodiment
Embodiment 1:
Weight percent (Wt%) C:0.05, Co:19.0, Cr:16, Ti:3.1, Al:1.3, Zr:0.07, Mn:0.20, B:0.007, the Ni of each component of material of the present invention: surplus.
Get each component materials by said ratio, prepare high-strength high-plasticity Ni-Cr-Co base turbine dish blade material in accordance with the following methods:
1) by the proportion ingredient of above-described embodiment;
2) step 1) described in batching, vacuum oven 2 refinings at 1530 ~ 1560 DEG C, first time refining at the temperature of (1530 ~ 1560) ± 5 DEG C, vacuum degree control at 1 ~ 0.1Pa, refining 10 ~ 20 minutes;
Second time refining is at the temperature of (1530 ~ 1560) ± 5 DEG C, and vacuum degree control is at 0.1 ~ more than 0.002Pa, and refining 10 minutes, with control composition segregation, then carries out induction stirring;
3) adopt thread middling speed evenly to pour into a mould on the molten steel of vacuum induction melting, the duration of pouring is 12 ~ 18 seconds, and teeming temperature control temperature is to DEG C obtaining resmelting electrode rod first in (1530 ~ 1560) ± 5; Accomplish during cast that low temperature is at the uniform velocity poured into a mould, and obtains resmelting electrode rod as far as possible.
4) resmelting electrode rod obtains the thermal treatment of alloy pig homogenizing through vacuum consumable remelting, is forged into the bar of high-strength high-plasticity Ni-Cr-Co base turbine dish blade material.
Described bar specification is diameter of phi 20mm ~ Φ 400mm.Wherein, the heat treated temperature of homogenizing is 1170 DEG C, and diameter is greater than the bar of 200mm, determines total soaking time by 1mm soaking time 1.5min; Be less than 200mm alloy pig for diameter, soaking time is 5h.
During forging bar, beginning forging 1180 DEG C, finish-forging is not less than 1000 DEG C, and bar will through button circle, alignment.Forging adds man-hour, expects to heat up with stove, and hot worked scope is 1000 ~ 1180 DEG C, due to 750 ~ 900 DEG C be carbide, σ phase, Laves phase, λ 1 separate out scope with χ phase, forbid below 950 DEG C, continue processing, otherwise have the danger of cracking.Single forging ratio is not less than 3.The bar specification of forging is that diameter of phi 20mm is as Φ 400mm.
Bar processing, finishing, flaw detection
Adopt detector device equipment to carry out inside and outside quality to detect, use all kinds of press to carry out finishing, keep good linearity and the linear lag.
Precise bar adopts high-performance bar special purpose lathe to carry out precision sizing, controls rotating speed and cutter speed, keeps high precision, the high smooth finish of bar.
The present embodiment prepares the bar of high-strength high-plasticity Ni-Cr-Co base turbine dish blade material, through following process turbine disk blade, can be used for petrochemical complex flue gas turbine expander.
By experiment, room-temperature mechanical property after resulting materials 1060 DEG C of solid solutions in 1 hour+200 hours 800 DEG C of Long-term Agings: Rm=1210MPa, Rp0.2=865MPa, A=24%, Z=36%; Solid solution state HV5=224; 870 DEG C, Rm:200MPa, τ >=80h, A (5D or 50mm) 7.5%.
Weight percent (Wt%) C:0.06 of each component of embodiment 2 material of the present invention, Co:20.0, Cr:17, Ti:3.2, Al:1.4, Zr:0.08, Mn:0.20, B:0.008, Ni: be surplus, according to the preparation method described in embodiment 1, obtain the bar of high-strength high-plasticity Ni-Cr-Co base turbine dish blade material, can be used for aero-turbine machine, turbine of calming the anger.
By experiment, room-temperature mechanical property after resulting materials 1060 DEG C of solid solutions in 1 hour+200 hours 800 DEG C of Long-term Agings: Rm=1260MPa, Rp0.2=910MPa, A=22%, Z=32%; Solid solution state HV5=230; 870 DEG C, Rm=200MPa, τ >=80h, A (5D or 50mm) 7.0%.900 DEG C, 100 hours antioxygen rates are 0.08g/m
2.h.
Embodiment 3: weight percent (Wt%) C:0.07 of each component of material of the present invention, Co:21.0, Cr:18, Ti:3.4, Al:1.5, Zr:0.08, Mn:0.20, B:0.009, Ni: surplus, according to the preparation method described in embodiment 1, obtain the bar of high-strength high-plasticity Ni-Cr-Co base turbine dish blade material, can be used for space flight, turbine turbine disk blade is calmed the anger in navigation.
By experiment, room-temperature mechanical property after resulting materials 1060 DEG C of solid solutions in 1 hour+200 hours 800 DEG C of Long-term Agings: Rm=1280MPa, Rp0.2=930MPa, A=20%, Z=29%; Solid solution state HV5=240; 870 DEG C, Rm=200MPa, τ >=80h, A (5D or 50mm) 6.5%.900 DEG C, 100 hours antioxygen rates are 0.08g/m
2.h.
Claims (10)
1. a material for high-strength high-plasticity Ni-Cr-Co base, is characterized in that, the weight percent of each component is:
Cr:15.50 ~ 19.50%; Co:18.0 ~ 21.0%; Ti:3.1 ~ 3.4%%; Al:1.3 ~ 2.0%; Zr≤0.15; B≤0.02%; Mn≤1.0%; C:0.05 ~ 0.07%; P≤0.004%; S≤0.004%, Si≤1.0%; Fe≤2.0%; Cu≤0.2%; Impurity≤0.015%; Surplus is nickel.
2. material according to claim 1, is characterized in that, the weight percent of each component is: C:0.05 ~ 0.07%, Co:19 ~ 21%, Cr:16 ~ 18%, Ti:3.1 ~ 3.4%, Al:1.3 ~ 1.5%, Zr≤0.08, Mn≤0.20, B≤0.009, P≤0.004%; S≤0.004%, Si≤1.0%; Fe≤2.0%; Cu≤0.2%; Impurity≤0.015%; Surplus is nickel.
3. material according to claim 1 and 2, is characterized in that: described impurity is Pb, As, Sb, Sn, Zn, Bi.
4. the preparation method of high-strength high-plasticity Ni-Cr-Co sill, is characterized in that, has following steps:
1) by the proportion ingredient described in claim 1 or 2;
2) step 1) described in batching, vacuum oven 2 refinings at 1530 ~ 1560 DEG C, stir, thread middling speed evenly pours into a mould 12 ~ 18 seconds, obtains resmelting electrode rod;
3) step 2) described in resmelting electrode rod obtain the thermal treatment of alloy pig homogenizing through vacuum consumable remelting, be forged into the bar for turbine disk blade material.
5. preparation method according to claim 4, is characterized in that: step 2) first time refining time in described 2 refinings is 10 ~ 20 minutes, vacuum tightness is 1 ~ 0.1Pa; Second time refining time is 10 minutes, vacuum tightness 0.1 ~ 0.002Pa.
6. preparation method according to claim 4, is characterized in that: step 3) described vacuum consumable remelting time be filled with helium, when being filled with helium, vacuum tightness≤6.5Pa.
7. preparation method according to claim 4, is characterized in that: step 3) described in homogenizing heat-treating methods be holding temperature 1170 DEG C, diameter is greater than the alloy pig of 200mm, and soaking time is every 1mm soaking time is 1.5min; Diameter is less than 200mm alloy pig, and soaking time is 5h.
8. preparation method according to claim 4, is characterized in that: step 3) initial forging temperature of described forging is 1180 DEG C, finish-forging >=1000 DEG C.
9. preparation method according to claim 4, is characterized in that: step 3) gained bar need forge processing, finishing, and forging adds man-hour, and bar heats up with stove, and the temperature of processing is 1000 ~ 1180 DEG C.
10. preparation method according to claim 4, is characterized in that: step 3) described bar specification is diameter of phi 20mm ~ Φ 400mm.
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