CN103882341B - A kind of antiwear heat resisting alloy material and preparation method thereof - Google Patents
A kind of antiwear heat resisting alloy material and preparation method thereof Download PDFInfo
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- CN103882341B CN103882341B CN201410109667.5A CN201410109667A CN103882341B CN 103882341 B CN103882341 B CN 103882341B CN 201410109667 A CN201410109667 A CN 201410109667A CN 103882341 B CN103882341 B CN 103882341B
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Abstract
The invention discloses a kind of antiwear heat resisting alloy material and preparation method thereof, high wear resistant hard is uniformly distributed in the thin brilliant austenitic matrix of resistance to high temperature oxidation by this material mutually.Obtaining austenitic matrix by adding Cr, Ni, adding Y base rare earth, formation oxide compacting is combined closely with matrix simultaneously, adding W object is form W displacement (Cr, Fe)
7c
3, (Cr, Fe)
23c
6middle Fe, Cr element and being solid-solution in (Cr, Fe)
7c
3, (Cr, Fe)
23c
6in, improve (Cr, Fe)
7c
3, (Cr, Fe)
23c
6hardness; Add Nb and form Hard Inclusion compound, Nb is as crystallization nuclei crystal grain thinning simultaneously, eliminates dentrite and improve carbide morphology, further crystal grain thinning in conjunction with vibration clotting method.Adopt this patent can significantly improve high temperature steel performance, wherein 1000 DEG C time hardness improve 10 ~ 15%, intensity improve 10 ~ 18%, oxidation weight gain reduce by 18 ~ 20%, work-ing life improves 20 ~ 25%.
Description
Technical field
The invention belongs to wear heat-resistant steel Material Field, relate to antiwear heat resisting alloy, especially a kind of antiwear heat resisting alloy material and preparation method thereof.
Background technology
The industrial equipment key parts such as electric power, metallurgy, cement, building materials, chemical industry bear high temperature oxidation and medium erosive wear operating mode, wash away as power industry bocca bears coal charge under worst hot case; Metallurgy industry grid section bears 1000 DEG C of high temperature in conveying slag, bears the wearing and tearing of slag simultaneously; Cement industry grate plate bears the erosive wear of cement under 1000 DEG C of worst hot cases; Chemical petroleum cracking tube bears washing away of medium in nearly 1000 DEG C of hot environments.Above-mentioned component failure mechanism, a kind of failure behaviour under high temperature oxidation and wearing and tearing interaction, form oxide film at high temperature oxidation, under medium souring, oxide film is washed wearing and tearing, new surface exposes, form oxide film again, the new oxide film formed is worn again, and the oxide film that goes round and begins again is formed and wearing and tearing, under high temperature wear operating mode, oxidation and wearing and tearing interaction, therefore just require that not only alloy material anti-oxidant but also wear-resistant.Distribute Hard Inclusion carbide in heat-stable material matrix; high rigidity carbide rises and resistance to wears function and protrude from matrix; bear key wear function; matrix supports carbide and does not come off; the carbide simultaneously protruding matrix has shielding effect to matrix; protection matrix, not by heavy wear, requires that matrix forms oxide compacting and is combined closely with matrix simultaneously, not easily wears away.Thus heat-stable material organizational requirements, matrix has high antioxidant property, and containing Cr, Ni austenite, Dispersed precipitate Hard Inclusion High-temperature-resandant andant wear-resistant carbide on matrix, needs matrix grain refinement for forming equally distributed Hard Inclusion carbide.
According to patent retrieval that applicant does, the method forming Hard Inclusion about heat-stable material grain-refining agent has following patent:
About rare-earth and high chromium, high nickel heat-resisting steel and preparation method thereof, patent No. CN101824583A is for mixed fire coal bocca material, main component element: Cr:28%-35%, Ni:25%-35%, Ti:0.3%-0.6%, Re:0.001%-0.1%, effect is passable, but high containing Ni, Cr, production cost is high, and can not strengthen M
7c
3or M
23c
6type carbide.
Following patent is had about vibration clotting:
China national Department of Intellectual Property granted patent CN103131960A(Rare earth heat-resistant steel), for coke oven grate bars selected materials: C:0.3%-0.4%, Si:1.3%-2%, Mn:0.8%-1.5%, Ni:7%-8.5%, Cr:24%-28%, S≤0.03%, P≤0.045, all the other are W and other trace elements, this patent principal feature is high containing W, and therefore production cost is high.
China national Department of Intellectual Property granted patent CN1316540A(high temperature steel), this patent material, except containing except C, Cr, Ni, Fe principal element, adds Nb, Ti, Co, B, Al, Ca, Mg, Nd element.This patent element is many, and production technique is difficult to control, and brings difficulty to material recovery.
China national Department of Intellectual Property granted patent CN101649424A(New Heat-Resistant Steel), this patent C:0.65%-0.75%, Si:0.7%-1.0%, Mn:1.0%-1.2%, Cr:18%-29%, Ni:20.5%-21%, Mo:0.55%-0.6%, other are containing Al, V, Co, Ti, Nb, W, Bi, Ca, B etc., can see that this patent contains Ni, Mo from composition high, production cost is high, high containing C, thermal shock resistance is poor.
Chinese invention patent CN102181746A adopts lost foam casting vibration clotting method refinement casting crystalline grain, effective, but adopts lost foam, and prepare foam etc., technical process is long, and cost is high.
Chinese invention patent CN102744367A adopts evaporative pattern shell moulded casting vibration clotting method crystal grain thinning, effective, but adopts evaporative pattern shell mould method to prepare foam, shell mould etc., and technical process is long, and cost is high.
Summary of the invention
The object of the invention is to the shortcoming overcoming above-mentioned prior art, a kind of antiwear heat resisting alloy material and preparation method thereof is provided, it is designed by material composition and preparation method forms material against oxidative performance, the high rigidity particle carbide of grain refining and even dispersion thereof, realizes having anti-oxidant, wear resistance concurrently.
The object of the invention is to be achieved through the following technical solutions:
First the present invention proposes a kind of antiwear heat resisting alloy material, is thin brilliant austenitic matrix high wear resistant hard being uniformly distributed in mutually resistance to high temperature oxidation.
Further, above-mentioned materials comprises the chemical composition of following mass percent:
C:0.2%-0.4%, Cr:20%-30%, Ni:7%-15%, Si:1.0%-3.0%, Mn:1.0%-3.0%, P≤0.03%, S≤0.03%, W:0.3%-1.0%, Nb:0.05%-1.5%, Y base rare earth: 0.1%-0.4%, Ca:0.003%-0.0045%, Al:0.04%-0.06%, surplus is Fe.
Further, the chemical composition C:0.2%-0.3% of mass percent, Cr:20%-25%, Ni:11%-13%, Si:1.5%-2.8%, Mn:1.8%-2.5%, W:0.5%-0.8%, Nb:0.08%-0.2%, Y base rare earth: 0.2%-0.3%, P≤0.04%, S≤0.04%, surplus is Fe.
The present invention also proposes a kind of preparation method of above-mentioned antiwear heat resisting alloy material, draws together following steps:
1) waste stainless steel, low carbon ferrochromium, nickel plate, ferrosilicon, ferromanganese, ferrotungsten are placed in induction furnace melting; Adopt ferrosilicon, ferromanganese, aluminum precipitation deoxidation, with silicon-calcium diffusive deoxidation refining, smelting temperature 1600 DEG C-1650 DEG C, ferro-niobium, Y base rare earth are placed in and are baked to 800 DEG C of ladles, ferro-niobium, Y base rare earth granularity are 1mm-3mm;
2) casting mold sand, makes binding agent with water glass, and carbonic acid gas makes solidifying agent, mo(U)ld face brushing Zircon powder alcohol group dope;
3) by mould assembling and closing, lock case, is fixed on vibrating device platform, opens vibrating device, casting of molten metal, teeming temperature 1530 DEG C-1580 DEG C, vibrational frequency 10HZ-60HZ, amplitude 0.5mm-2mm, after casting solidification, closes vibrating device;
4) after foundry goods cooling, rising head and running channel is cut away, polishing cleaning overlap.
Above-mentioned casting mold sand is quartz sand.
Above-mentioned mould assembling and closing is placed on the shaking platform of vibration equipment together with sandbox.
Further, above-mentioned pouring temperature range 1530 DEG C-1570 DEG C.
The present invention obtains austenitic matrix by adding Cr, Ni, adds Y base rare earth, and formation oxide compacting is combined closely with matrix simultaneously, and adding W object is form W displacement (Cr, Fe)
7c
3, (Cr, Fe)
23c
6middle Fe, Cr element and being solid-solution in (Cr, Fe)
7c
3, (Cr, Fe)
23c
6in, improve (Cr, Fe)
7c
3, (Cr, Fe)
23c
6hardness; Add Nb and form Hard Inclusion compound, Nb is as crystallization nuclei crystal grain thinning simultaneously, eliminates dentrite and improve carbide morphology, further crystal grain thinning in conjunction with vibration clotting method.The present invention has following beneficial effect:
1) adopt the present invention can obtain high temperature resistant austenitic matrix, surface forms fine and close oxidation-resistant film, improves thermotolerance;
2) this patent is adopted to obtain the M containing W of high rigidity
7c
3or M
20c
5type compound, improves high temperature abrasion resistance;
3) adopt this patent obtain thin crystalline substance and significantly reduce dentrite tissue, improve high temperature steel obdurability;
4) adopt the present invention can significantly improve high temperature steel performance, wherein 1000 DEG C time hardness improve 10 ~ 15%, intensity improve 10 ~ 18%, oxidation weight gain reduce by 18 ~ 20%, work-ing life improves 20 ~ 25%.
Accompanying drawing explanation
Fig. 1 be in embodiment 1 structural state figure wherein (a) for not vibrate, (b) for vibration;
Fig. 2 be in embodiment 2 structural state figure wherein (a) for not vibrate, (b) for vibration;
Fig. 3 be in embodiment 3 structural state figure wherein (a) for not vibrate, (b) for vibration.
Embodiment
Antiwear heat resisting alloy material of the present invention is thin brilliant austenitic matrix high wear resistant hard being uniformly distributed in mutually resistance to high temperature oxidation.This kind of material comprises the chemical composition of following mass percent: C:0.2%-0.4%, Cr:20%-30%, Ni:7%-15%, Si:1.0%-3.0%, Mn:1.0%-3.0%, P≤0.03%, S≤0.03%, W:0.3%-1.0%, Nb:0.05%-1.5%, Y base rare earth: 0.1%-0.4%, Ca:0.003%-0.0045%, Al:0.04%-0.06%, surplus is Fe.
In preferred version of the present invention, the chemical composition of above mass percent can be optimized for further: C:0.2%-0.3%, Cr:20%-25%, Ni:11%-13%, Si:1.5%-2.8%, Mn:1.8%-2.5%, W:0.5%-0.8%, Nb:0.08%-0.2%, Y base rare earth: 0.2%-0.3%, P≤0.04%, S≤0.04%, and surplus is Fe.In alloy material, Nb, Y element obtain, and after liquid steel refining, put in ladle by Nb-Fe alloy, Y base rare earth, granularity is 1mm-3mm, and baking temperature of steel ladle is not less than 800 DEG C.
The preparation method of antiwear heat resisting alloy material of the present invention comprises the following steps:
1) waste stainless steel, low carbon ferrochromium, nickel plate, ferrosilicon, ferromanganese, ferrotungsten are placed in induction furnace melting; Adopt ferrosilicon, ferromanganese, aluminum precipitation deoxidation, with silicon-calcium diffusive deoxidation refining, smelting temperature 1600 DEG C-1650 DEG C, ferro-niobium, Y base rare earth are placed in and are baked to 800 DEG C of ladles, ferro-niobium, Y base rare earth granularity are 1mm-3mm;
2) binding agent made by casting mold quartz sand type selecting water glass, and carbonic acid gas makes solidifying agent, mo(U)ld face brushing Zircon powder alcohol group dope;
3) by mould assembling and closing, lock case, is fixed on vibrating device platform, opens vibrating device, casting of molten metal, teeming temperature 1530 DEG C-1580 DEG C, vibrational frequency 10HZ-60HZ, amplitude 0.5mm-2mm, after casting solidification, closes vibrating device.
4) after foundry goods cooling, rising head and running channel is cut away, polishing cleaning overlap.
As mentioned above, alloy material of the present invention is suitable solidifies under vibrating conditions.Antiwear heat resisting component Foundry quartz sand is quartz sand, and binding agent is water glass, by carbon dioxide solidification, and external coating Zircon powder alcohol group dope.Mould assembling and closing is placed on the shaking platform of vibration equipment together with sandbox, and open vibration equipment during cast, casting solidification after vibration terminates.Teeming temperature can control further between 1530 DEG C-1570 DEG C.
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail:
Embodiment 1:
1. composition: C:0.3%, Cr:24%, Ni:11.5%, Si:2.6%, Mn:2.0%, P and S≤0.03%, W:0.6%, Nb:0.1%, Y base rare earth 0.2%.
2. waste stainless steel, low carbon ferrochromium, nickel plate, ferrosilicon, ferromanganese, ferrotungsten are placed in induction furnace melting; Adopt ferrosilicon, ferromanganese, aluminum precipitation deoxidation, with silicon-calcium diffusive deoxidation refining, smelting temperature is 1620 DEG C, and ferro-niobium, Y base rare earth are placed in ladle, granularity 1-3mm, and ladle is baked to and is not less than 800 DEG C.
3. casting mold quartz sand, water glass makees binding agent, carbon dioxide solidification, mo(U)ld face brush zircon flour coating, mould assembling, lock case.
4. the casting mold after lock case being placed on vibrating device platform together with sandbox, opening vibration device, Pour Steel, closing vibration, vibration parameters to solidifying completely: frequency 25HZ, amplitude 1mm.
5. teeming temperature 1560 DEG C.
Hardness 38HV, σ during material of the present invention 1000 DEG C after tested
1000 1000for 15MPa, oxidation weight gain 48g/cm
2, compare ZG
40cr
25ni
20hardness, σ 1000 DEG C time
1000 1000improve 15% and 10% respectively, oxidation weight gain compares ZG
40cr
25ni
20reduce by 18%, obviously reduce, as Fig. 1 through vibration dentrite.Thermal power plant's bocca life-span of preparing by this material and method compares ZG
40cr
25ni
20improve 25%.
Embodiment 2:
1. composition: C:0.25%, Cr:25%, Ni:12%, Si:2.2%, Mn:1.8%, P and S≤0.03%, W:0.7%, Nb:0.12%, Y base rare earth 0.25%.
2. waste stainless steel, low carbon ferrochromium, nickel plate, ferrosilicon, ferromanganese, ferrotungsten are placed in induction furnace melting; Adopt ferrosilicon, ferromanganese, aluminum precipitation deoxidation, with silicon-calcium diffusive deoxidation refining, ferro-niobium, Y base rare earth are placed in ladle, degree of depth 1-3mm by smelting temperature 1610 DEG C, and ladle is baked to and is not less than 800 DEG C.
3. casting mold quartz sand, water glass makees binding agent, carbon dioxide solidification, mo(U)ld face brush zircon flour coating, mould assembling, lock case.
4. the casting mold after lock case being placed on vibrating device platform together with sandbox, opening vibration device, Pour Steel, closing vibration, vibration parameters to solidifying completely: frequency 20Hz, amplitude 0.8mm.
5. teeming temperature 1550 DEG C.
Hardness 35HV, σ during material of the present invention 1000 DEG C after tested
1000 1000for 19MPa, oxidation weight gain 45g/cm
2, hardness, σ 1000 DEG C time
1000 1000value and ZG
40cr
25ni
20compare and improve 10% and 18% respectively, oxidation weight gain compares ZG
40cr
25ni
20reduce by 20%, compared with not vibrating, this invention material dentrite obviously reduces, as Fig. 2.The grate plate prepared with material of the present invention and method (cement grate-cooler with) compares ZG work-ing life
40cr
25ni
20the raising 21% made.
Embodiment 3
1. composition: C:0.28%, Cr:23%, Ni:11%, Si:2%, Mn:2.0%, P and S≤0.03%, W:0.4%, Nb:0.08%, Y base rare earth 0.2%.
2. waste stainless steel, low carbon ferrochromium, nickel plate, ferrosilicon, ferromanganese, ferrotungsten are placed in induction furnace melting; Adopt ferrosilicon, ferromanganese, aluminum precipitation deoxidation, with silicon-calcium diffusive deoxidation refining, smelting temperature 1600 DEG C; Ferro-niobium, Y base rare earth are placed in ladle, granularity 1mm-3mm, and ladle is baked to and is not less than 800 DEG C.
3. casting mold quartz sand, water glass makees binding agent, carbon dioxide solidification, mo(U)ld face brush zircon flour coating, mould assembling, lock case.
4. the casting mold after lock case being placed on vibrating device platform together with sandbox, opening vibration device, Pour Steel, closing vibration, vibration parameters to solidifying completely: frequency 30HZ, amplitude 1mm.
5. teeming temperature 1540 DEG C.
Hardness 36HV, σ during material of the present invention 1000 DEG C after tested
1000 1000for 16MPa, oxidation weight gain 46g/cm
2, compare ZG
40cr
25ni
20hardness, σ 1000 DEG C time
1000 1000value improves 12% and 17% respectively, and oxidation weight gain compares ZG
40cr
25ni
20reduce by 18%, obviously reduce than the dentrite do not vibrated, as Fig. 3 through vibration.This invention material dentrite obviously reduces, as Fig. 3.
Grid section ratio in the work-ing life ZG prepared with material of the present invention and method
40cr
25ni
20the raising 20% made.
The effective constituent design considerations of wear heat-resistant material of the present invention and the reason of content range as follows:
C: carbon is the important element in wear heat-resistant material steel, be the element expanding austenite phase, C and Cr, W, Nb form high rigidity carbide and improve wear resistance, but the carbon being solid-solution in high temperature steel can not be high, otherwise oxidation-resistance, corrodibility are poor, toughness is low and wear no resistance.Along with the change of Cr, W, Nb, the composition range of carbon selects 0.2%-0.4% more suitable.
Cr: chromium is alloying element important in heat-resistant antifriction steel part, higher chromium content can make steel surface form finer and close Cr
2o
3film protection steel part, improves the antioxidant anticorrosive ability of antiwear heat resisting steel part.Higher chromium content also helps the solid solution purification of steel simultaneously, and suitable carbide is formed, and then improves hot strength, hardness and the wear resisting property of steel.The content selection of Cr is more suitable at 20%-30%.
Ni: nickel is the main alloy element expanding Ovshinsky phase stabilizer in steel, but in steel, carbon, manganese etc. expand the element of austenite phase, and thus the nickel content obtained needed for austenite structure can reduce, and to reduce costs, therefore nickel range of choice is at 7%-15%.
Si: the effect of silicon easily forms oxidation resistant SiO
2oxide film; in steel, silicon and the element reaction such as oxygen, chromium form the oxide film of protectiveness, thus significantly improve the high temperature oxidation resistance of steel, suitably increase silicon also favourable to the casting fluidity of wear heat-resistant steel; but the too high remarkable reduction intensity of silicon, the suitable range of choice 1 ~ 3% of silicon.
Mn: manganese is the alloying element expanding Ovshinsky phase stabilizer, in wear heat-resistant steel, manganese replaces nickel to a certain extent, manganese has the effect of solution strengthening, intensity and the hardness of steel can be improved, when same chromium content, resistance of oxidation DIFFERENT Cr-the nickel steel of manganese-Mn austenitic steel, but in sulphur atmosphere, the austenite corrosion-resistant of Fu Meng is better than the austenite of rich nickel.Therefore, the optimum range of manganese is 1%-3%.
W: tungsten is carbide forming element, can significantly improve wear resistance, is especially solid-solution in (CrFe)
7c
3(CrFe)
23c
6compound formation is containing (CrFeW) of W
7c
3(CrFeW)
23c
6in can significantly improve its wear resistance, the W be simultaneously solid-solution in matrix can improve thermotolerance.NbC effectively to be suppressed in high-temperature service process to the transformation of Ni16Nb6Si7 by adding W, thus improve the high temperature creep property of alloy.But the too high easy segregation of W, therefore the range of choice of W is 0.3%-1%.
Y base rare earth: the binding ability that can significantly improve corrosion products film density and film and matrix, and then improve corrosion resisting property.
Nb: niobium is carbide, is conducive to the precipitation hardening of wear heat-resistant steel, thus the hot strength of raising steel, hardness and wear resistance.The niobium of trace also has the effect of obvious refinement antiwear heat resisting crystalline grain of steel.
P, S: p and s is harmful element in wear heat-resistant steel.
Claims (4)
1. a preparation method for antiwear heat resisting alloy material, is characterized in that, the high wear resistant hard of described antiwear heat resisting alloy material is uniformly distributed in the thin brilliant austenitic matrix of resistance to high temperature oxidation mutually, and it comprises the chemical composition of following mass percent:
C:0.2%-0.3%, Cr:20%-25%, Ni:11%-13%, Si:1.5%-2.8%, Mn:1.8%-2.5%, W:0.5%-0.8%, Nb:0.08%-0.2%, Y base rare earth: 0.2%-0.3%, P≤0.04%, S≤0.04%, surplus is Fe;
Comprise the following steps:
1) waste stainless steel, low carbon ferrochromium, nickel plate, ferrosilicon, ferromanganese, ferrotungsten are placed in induction furnace melting; Adopt ferrosilicon, ferromanganese, aluminum precipitation deoxidation, with silicon-calcium diffusive deoxidation refining, smelting temperature 1600 DEG C-1650 DEG C, ferro-niobium, Y base rare earth are placed in the ladle being baked to and being not less than 800 DEG C, ferro-niobium, Y base rare earth granularity are 1mm-3mm;
2) casting mold sand, makes binding agent with water glass, and carbonic acid gas makes solidifying agent, mo(U)ld face brushing Zircon powder alcohol group dope;
3) by mould assembling and closing, lock case, is fixed on vibrating device platform, opens vibrating device, casting of molten metal, teeming temperature 1530 DEG C-1580 DEG C, vibrational frequency 10HZ-60HZ, amplitude 0.5mm-2mm, after casting solidification, closes vibrating device;
4) after foundry goods cooling, rising head and running channel is cut away, polishing cleaning overlap.
2. the preparation method of antiwear heat resisting alloy material according to claim 1, it is characterized in that, casting mold sand is quartz sand.
3. the preparation method of antiwear heat resisting alloy material according to claim 1, it is characterized in that, mould assembling and closing is placed on the shaking platform of vibration equipment together with sandbox.
4. the preparation method of antiwear heat resisting alloy material according to claim 1, is characterized in that, pouring temperature range 1530 DEG C-1570 DEG C.
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| CN105803339B (en) * | 2016-04-06 | 2017-11-28 | 广东省材料与加工研究所 | A kind of heat-resistance abrasion-resistance alloy steel and preparation method thereof |
| CN107245648B (en) * | 2017-06-02 | 2019-03-19 | 江阴国润机械有限公司 | High-temperature wearable fire grate segment and its casting mold and pouring technology |
| CN107354394A (en) * | 2017-09-11 | 2017-11-17 | 广东省材料与加工研究所 | A kind of boracic wear-resisting alloy steel and preparation method thereof |
| CN109856005A (en) * | 2018-12-25 | 2019-06-07 | 力信（江苏）能源科技有限责任公司 | A kind of cell size solid content test device and test method |
| CN114686781B (en) * | 2022-05-31 | 2022-12-06 | 苏州集萃高合材料科技有限公司 | Austenitic stainless steel and preparation and processing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223214A (en) * | 1992-07-09 | 1993-06-29 | Carondelet Foundry Company | Heat treating furnace alloys |
| CN101649424A (en) * | 2009-08-18 | 2010-02-17 | 泰州市永昌冶金设备有限公司 | Novel heat resistant steel |
| WO2013131811A1 (en) * | 2012-03-07 | 2013-09-12 | Mahle International Gmbh | Heat-resistant bearing material made of an austenitic iron matrix alloy |
-
2014
- 2014-03-21 CN CN201410109667.5A patent/CN103882341B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223214A (en) * | 1992-07-09 | 1993-06-29 | Carondelet Foundry Company | Heat treating furnace alloys |
| CN101649424A (en) * | 2009-08-18 | 2010-02-17 | 泰州市永昌冶金设备有限公司 | Novel heat resistant steel |
| WO2013131811A1 (en) * | 2012-03-07 | 2013-09-12 | Mahle International Gmbh | Heat-resistant bearing material made of an austenitic iron matrix alloy |
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