CN101580913B - High-chromium cast iron composite inoculant, preparation method and application thereof - Google Patents
High-chromium cast iron composite inoculant, preparation method and application thereof Download PDFInfo
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- CN101580913B CN101580913B CN2009100683341A CN200910068334A CN101580913B CN 101580913 B CN101580913 B CN 101580913B CN 2009100683341 A CN2009100683341 A CN 2009100683341A CN 200910068334 A CN200910068334 A CN 200910068334A CN 101580913 B CN101580913 B CN 101580913B
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- 229910001018 Cast iron Inorganic materials 0.000 title claims abstract description 254
- 239000011651 chromium Substances 0.000 title claims abstract description 244
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 243
- 239000002054 inoculum Substances 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 201
- 239000000956 alloy Substances 0.000 claims abstract description 201
- 238000005266 casting Methods 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 70
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 51
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 51
- 238000007670 refining Methods 0.000 claims abstract description 50
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims abstract description 48
- 229910008455 Si—Ca Inorganic materials 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000010791 quenching Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000003672 processing method Methods 0.000 claims abstract description 4
- 239000002667 nucleating agent Substances 0.000 claims description 53
- 229910052796 boron Inorganic materials 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 229910052750 molybdenum Inorganic materials 0.000 claims description 25
- 239000011733 molybdenum Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 230000000171 quenching effect Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000005422 blasting Methods 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 238000009395 breeding Methods 0.000 claims description 8
- 230000001488 breeding effect Effects 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 238000007669 thermal treatment Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000007872 degassing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000004567 concrete Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 150000002751 molybdenum Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 23
- 239000011159 matrix material Substances 0.000 abstract description 22
- 229910001567 cementite Inorganic materials 0.000 abstract description 9
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract 1
- 230000005496 eutectics Effects 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 16
- 210000001787 dendrite Anatomy 0.000 description 14
- 150000001247 metal acetylides Chemical class 0.000 description 14
- 230000000630 rising effect Effects 0.000 description 14
- 239000011575 calcium Substances 0.000 description 8
- 238000009377 nuclear transmutation Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001349 ledeburite Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000006025 fining agent Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 230000008520 organization Effects 0.000 description 4
- 229910000604 Ferrochrome Inorganic materials 0.000 description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- OOJQNBIDYDPHHE-UHFFFAOYSA-N barium silicon Chemical compound [Si].[Ba] OOJQNBIDYDPHHE-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910017082 Fe-Si Inorganic materials 0.000 description 2
- 229910017133 Fe—Si Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910001037 White iron Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 229910000939 field's metal Inorganic materials 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000003437 strontium Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
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Abstract
The invention relates to a high-chromium cast iron composite inoculant, a preparation method and an application thereof, in particular to cast iron alloy containing chromium. The high-chromium cast iron composite inoculant is a nanocrystalline high-chromium cast iron composite inoculant containing rare-earth ferrosilicon and ferroboron. The high-chromium cast iron composite inoculant comprises Fe-Ce-Si-Ca intermediate alloy and Fe-B intermediate alloy, wherein the weight ratio between the Fe-Ce-Si-Ca intermediate alloy and the Fe-B intermediate alloy is 1:0.07-0.13. The nanocrystalline crystalgrains of the inoculant are less than 100nm, the inoculant is a flaky inoculant obtained by carrying out melt fast-quenching processing on raw materials which comprise commercially purchased rare-ear th ferrosilicon and commercially purchased ferroboron, the inoculant is used for carrying out crystal grain and tissue refining processing on the tissue of the high-chromium cast iron alloy of high-chromium cast iron wear parts used for engineering machinery, the processing method is a metal melt casting method, the casting defect of the existing casting technology of the high-chromium cast iron alloy is overcame, and matrix crystal grains and cementite phases are obviously refined, so that the overall mechanical properties of the high-chromium cast iron alloy are obviously improved.
Description
Technical field
Technical scheme of the present invention relates to the cast iron alloy that contains chromium, specifically relates to high-chromium cast iron composite inoculant and its production and application.
Background technology
Along with engineering machinery such as paver, cement bituminous mixing plant, crusher, brick press and choosing/coal washing plant constantly develop, more and more harsher requirement has been proposed for the mechanical property of rich chromium cast iron wearing pieces such as the blade liner plate of its various models, blade, nose angle.For how improving mechanical property and the wearing and tearing corrosion resisting property of engineering machinery with the rich chromium cast iron wearing piece, the more existing experimental studies of relevant scholar and technician.In general high-chromium cast iron alloy as-cast structure, matrix crystal grain is thicker, and cementite in the eutectic ledeburite organization then presents thicker sheet mutually, and alloyed cementite mostly is thick polygonal shape and tabular mutually.Thick hard crisp cementite has quite seriously isolated matrix, has reduced the intensity and the toughness of high-chromium cast iron alloy.The high-chromium cast iron alloy as-cast structure being carried out grain refining handle, and change the form of cementite phase, reduce its weakening effect to substrate performance, is the effective way that improves high-chromium cast iron alloy as-cast structure performance.So it is a kind of extremely effective means that improves rich chromium cast iron wearing piece use properties that engineering machinery is carried out with the high-chromium cast iron alloy of rich chromium cast iron wearing piece that crystal grain and structure refinement handle.
Can influence the degree of high-chromium cast iron alloy grain size and structure refinement from two aspects: I. crystal grain and structure refinement are handled.The method of the concrete thinning processing of high-chromium cast iron alloy had to add breed fining agent (be inoculation modificator or claim the crystal grain modifying-refining agent, be called for short nucleating agent), ultrasonic vibration method, quench, low temperature casting or liquation pressure casting method.Wherein studying more method is to add to breed fining agent, this is to add a spot of fining agent that breeds in the high-chromium cast iron alloy melt, form a large amount of disperses, the infusible crystallization nuclei, and make the matrix melt when crystallization according to nucleus growth, thereby obtain grain refining and tissue thinning effect.The modifying-refining of high-chromium cast iron alloy is handled the intensity and the toughness that both can improve high-chromium cast iron alloy, can increase its wear resistance again, and then significantly improves the work-ing life that engineering machinery is used the rich chromium cast iron wearing piece; II. change melting technology.This is in the high-chromium cast iron alloy preparation process, by changing the purpose that this alloy crystallization condition reaches crystal grain thinning and tissue.
CN1115339 has disclosed Cr series white cast iron compound inoculant, and it contains C, Cr, Fe, Si, Mg, Re element in forming; CN87100402 discloses the nucleating agent of graphitic cast iron, be a kind of silicon-iron nucleating agent, contain during it is formed 0.1 to 10% (weight) strontium, less than 0.35% (weight) calcium and 0.1 to 15% (weight) zirconium, 0.1 to 20% (weight) titanium or and the mixture of zirconium and iron and this strontium; CN1281513 discloses the production method of iron casting inoculant and iron casting inoculant, and this nucleating agent contains the manganese of magnesium, the aluminium less than 5% (weight), 0-10% (weight) of the cerium of the calcium of silicon, 0.5-10% (weight) of 40-80% (weight) and/or strontium and/or barium, 0-10% (weight) and/or lanthanum, 0-5% (weight) and/or titanium and/or zirconium, the oxygen that is one or more metal oxide forms of 0.5-10% (weight), sulphur that is one or more metallic sulfide forms and the surplus of 0.1-10% (weight) is Fe; CN101319290 has disclosed graphitic cast iron nucleating agent and preparing product method and as the application of smelting cast iron, this nucleating agent is made up of ferrosilicon, ferromanganese, silicon barium or ferrochrome, wherein contains silicon, barium, manganese, aluminium, calcium, iron, or chromium, trace element.Method steps is: after ferrosilicon, ferromanganese, silicon barium or ferrochrome are carried out fragmentation respectively, the mixing of weighing in proportion, nucleating agent is as the application of smelting graphitic cast iron, the ratio of its molten iron and nucleating agent is 1: 0.03～0.07, nucleating agent lumpiness maximum value is ferrosilicon 10～20mm, silicon barium 20～30mm, ferromanganese 5～20mm, ferrochrome 1～15mm; CN1077229 discloses cast-iron compound inoculant, and it is made up of carbon, silicon, calcium, aluminium, chromium and balance iron.
The preparation method of the nucleating agent of being reported in the above-mentioned document all adopts broken explained hereafter of mixing a quasi-tradition, these nucleating agents then all adopt common melting technology melting and ingot casting are ground into fritter in the cast iron alloy Application in Casting and use, the grain-size of its fining agent far is not a nano level, so unsatisfactory to the thinning effect of cast iron alloy matrix grain and tissue.Facts have proved, the nucleating agent that these traditional technologys are produced is used for the high-chromium cast iron alloy tissue is carried out crystal grain and structure refinement processing, in the as-cast structure of the high-chromium cast iron alloy that passes through refinement, cementite in the eutectic ledeburite organization still is thicker sheet mutually, and the comprehensive mechanical property of high-chromium cast iron alloy can not get effective raising.
Summary of the invention
Technical problem to be solved by this invention is: high-chromium cast iron composite inoculant and its production and application is provided, high-chromium cast iron composite inoculant of the present invention is a kind of nanocrystalline rare-earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant, be to be that raw material carries out melt-spun and handles the sheet-like nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that makes by being purchased rare earth ferrosilicon+be purchased ferro-boron, engineering machinery is carried out crystal grain with the high-chromium cast iron alloy tissue of rich chromium cast iron wearing piece and structure refinement is handled with it, overcome the casting flaw of existing high-chromium cast iron alloy foundry engieering, matrix grain is able to remarkable refinement mutually with cementite, thereby has improved the comprehensive mechanical property of high-chromium cast iron alloy significantly.
The present invention solves this technical problem the technical scheme that is adopted: high-chromium cast iron composite inoculant, it is a kind of high-chromium cast iron composite inoculant of nanocrystalline rare earth ferrosilicon+ferro-boron, form by Fe-Ce-Si-Ca master alloy and Fe-B master alloy, wherein, the elementary composition of Fe-Ce-Si-Ca master alloy is 30.7%Fe+30%Ce+37.5%Si+1.8%Ca, the elementary composition of Fe-B master alloy is 78.61%Fe+20.76%B+0.35%Si+ impurity (0.108%Al+0.018%P+0.15%C+0.004%S), the weight ratio of these two kinds of master alloys is the Fe-Ce-Si-Ca master alloy: Fe-B master alloy=1: 0.07～0.13, the nanocrystalline crystal grain of this nucleating agent is less than 100nm.
Above-mentioned high-chromium cast iron composite inoculant is a kind of high-chromium cast iron composite inoculant of laminar nanocrystalline rare earth ferrosilicon+ferro-boron, and the mean thickness of this thin slice is 0.2～0.5mm, and width average is 0.3～0.7mm, and mean length is 0.8～1.5mm.
Above-mentioned Fe-Ce-Si-Ca master alloy and Fe-B master alloy are technical field alloy commonly used in the foundry industry, all can be commercially available.The metallographic structure pattern of these two kinds of master alloys as depicted in figs. 1 and 2.The grain-size that is purchased ferro-boron in the Fe-B master alloy as shown in Figure 1 is on average at 100 μ m; Be purchased the thick Fe-Si eutectic structure that exists in the rare earth ferrosilicon of Fe-Ce-Si-Ca master alloy greater than 200 μ m as shown in Figure 2.
The preparation method of high-chromium cast iron composite inoculant, be that a kind of centrifugal fast quenching gets rid of the band method, concrete steps are: with elementary composition be 30.7% Fe+30% Ce+37.5% Si+1.8% Ca be purchased the Fe-Ce-Si-Ca master alloy and elementary composition be that the Fe-B master alloy that is purchased of 78.61% Fe+20.76% B+0.35% Si+ impurity (0.108% Al+0.018% P+0.15% C+0.004%S) is a raw material, it is the Fe-Ce-Si-Ca master alloy by weight: Fe-B master alloy=1: 0.07～0.13, take by weighing the Fe-Ce-Si-Ca master alloy that is purchased of aequum and the Fe-B master alloy that is purchased, put into the water jacketed copper crucible of vacuum quick quenching furnace, regulate electrode position, make it and crucible in the raw alloy particle between distance be 0.5～1.5mm, close fire door, feed inlet and outlet and purging valve are evacuated to and are higher than 5 * 10
-3Behind the Pa, use ar purging, charge into argon gas to 0.04～0.05Pa subsequently, regulate arc current after the starting the arc and progressively rise to 500～600A, raw alloy in the crucible is melted, when treating that this alloy all is fused into liquid state, this crucible that tilts makes this alloy liquid cause on the water-cooled molybdenum wheel of high speed rotating by runner, molybdenum wheel edge line speed is 30～40m/ second, molybdenum wheel surface temperature is 10～15 ℃, this alloy liquid is with after this molybdenum wheel contact, solidifies rapidly and form thin ribbon shaped to take turns tangential direction along molybdenum and fly out, and falls into the boxroom of body of heater bottom after baffle plate stops, it is 0.2～0.5mm that fast quenching obtains mean thickness, width average is 0.3～0.7mm, and mean length is 0.8～1.5mm, and crystal grain is less than the high-chromium cast iron composite inoculant of laminar nanocrystalline rare earth ferrosilicon+ferro-boron of 100nm.
The application of above-mentioned high-chromium cast iron composite inoculant is to use it for the high-chromium cast iron alloy tissue is carried out crystal grain and structure refinement processing, and treatment process is the metal melting casting, and concrete steps are as follows:
The first step, batching
The batching first is the raw material of preparation rich chromium cast iron, and its chemical ingredients is that C=2.4～3.2%, Si≤1.2%, Mn≤1.2%, P≤0.05%, S≤0.05%, Cr=13～20%, Ni≤0.25%, V≤0.07%, B≤0.005% and all the other are Fe,
Batching second is the high-chromium cast iron composite inoculant of the above-mentioned laminar nanocrystalline rare earth ferrosilicon+ferro-boron of sealing preservation,
By weight being the batching first: batching second=100: 0.04～0.08 takes by weighing batching, guarantees all material drying in the operating process;
Second step, the fusing of high-chromium cast iron alloy and refining
Batching first in the first step is put into Medium Frequency Induction Heating Furnace crucible internal heating to 1480～1550 ℃, to the whole fusings of the first of preparing burden, the zinc chloride that is incorporated as batching first weight 2～3% carries out the degasification refining, remove gas and impurity in the batching first alloy melt, make the high-chromium cast iron alloy melt after the refining;
The 3rd step, refinement
Under the condition of the temperature of fusion in second step, add the batching second that by the first step takes by weighing in the high-chromium cast iron alloy melt after second goes on foot the refining that makes in insulation, left standstill 4～6 seconds after mechanical stirring is even, make the refining high-chromium cast iron alloy melt after breeding;
The 4th step, casting
With the 3rd the step make breed after refining high-chromium cast iron alloy melt leave standstill cooling, after being controlled at 1390～1430 ℃ to pouring temperature, refining high-chromium cast iron alloy melt after again this being bred is cast in the sand mold mould, place the impurity that filtering net is carried secretly with removing during casting on the mould, treat molding behind this high-chromium cast iron alloy melt solidifying, obtain the high-chromium cast iron alloy foundry goods;
The 5th step, thermal treatment
The high-chromium cast iron alloy foundry goods that the 4th step casting is obtained is 960 ± 10 ℃ of insulations 2～5 hours down in temperature, handles through oil cooling, and reheat to 300 ℃ carries out Shot Blasting and makes casting high-chromium cast iron alloy product after the tempered processing.
Percentage ratio in the aforesaid method is weight percentage, and oil cooling processing, temper and the Shot Blasting in the aforesaid method all is known processing methodes.
In the application of above-mentioned high-chromium cast iron composite inoculant, the said high-chromium cast iron alloy product that makes of the 5th step is engineering machinery high chrome cast iron lining plate wearing piece and a mechanical property standard test specimen thereof.
The invention has the beneficial effects as follows: in the fusion casting technique of engineering machinery with the high chrome cast iron lining plate wearing piece, add the high-chromium cast iron composite inoculant that is used for the high-chromium cast iron alloy tissue is carried out the nanocrystalline rare earth ferrosilicon+ferro-boron of crystal grain and structure refinement processing of the present invention, the high-chromium cast iron composite inoculant of this nanocrystalline rare earth ferrosilicon+ferro-boron has the acting in conjunction of rotten and refinement to the high-chromium cast iron alloy melt, make that the heterogeneous forming core heart significantly increases in the high-chromium cast iron alloy melt, the remarkable refinement of matrix grain, primary cementite phase and ledeburite organization in the rich chromium cast iron as-cast structure have obtained remarkable refinement, increased interfacial energy, thereby reduced the casting flaw of high-chromium cast iron alloy, the intensity and the toughness of high-chromium cast iron alloy have been improved, increased its wear resistance again, and then remarkable work-ing life of improving engineering machinery with the rich chromium cast iron wearing piece.In detail theoretical explanation and true offset information are seen table 1 in following examples and Fig. 3～10 and to their explanation.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the metallograph that is purchased the Fe-B master alloy.
Fig. 2 is the metallograph that is purchased the Fe-Ce-Si-Ca master alloy.
Fig. 3 is high-chromium cast iron composite inoculant transmission electron microscope of the present invention displaing micro tissue topography.
The metallographic structure contrast figure of the high-chromium cast iron alloy product sample that Fig. 4 makes under casting condition of the same race for the high-chromium cast iron composite inoculant that makes with traditional method among the embodiment 4 with nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that the inventive method makes.
Fig. 5 is high-chromium cast iron composite inoculant that makes with traditional method among the embodiment 4 and the rich chromium cast iron sample metallographic structure contrast figure of nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant under casting condition of the same race and same casting postheat treatment condition that makes with the inventive method.
The metallographic structure contrast figure of the high-chromium cast iron alloy product sample that Fig. 6 makes under casting condition of the same race for the high-chromium cast iron composite inoculant that makes with traditional method among the embodiment 5 with nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that the inventive method makes.
Fig. 7 is high-chromium cast iron composite inoculant that makes with traditional method among the embodiment 5 and the rich chromium cast iron sample metallographic structure contrast figure of nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant under casting condition of the same race and same casting postheat treatment condition that makes with the inventive method.
The metallographic structure contrast figure of the high-chromium cast iron alloy product sample that Fig. 8 makes under casting condition of the same race for the high-chromium cast iron composite inoculant that makes with traditional method among the embodiment 6 with nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that the inventive method makes.
Fig. 9 is high-chromium cast iron composite inoculant that makes with traditional method among the embodiment 6 and the rich chromium cast iron sample metallographic structure contrast figure of nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant under casting condition of the same race and same casting postheat treatment condition that makes with the inventive method.
Figure 10 is high-chromium cast iron composite inoculant that makes with traditional method among the embodiment 6 and the nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant eutectic carbides interlamellar spacing contrast figure in casting condition of the same race and the same rich chromium cast iron sample metallographic structure ledeburite of casting under the postheat treatment condition that makes with the inventive method.
Embodiment
Routine embodiment 1～3 discloses the centrifugal fast quenching for preparing high-chromium cast iron composite inoculant and has got rid of the band method down, the wherein used elementary composition 30.7%Fe+30%Ce+37.5% Si+1.8% Ca of being that is purchased the Fe-Ce-Si-Ca master alloy of three peak rare earth company limiteds of Baogang production, used the elementary composition of Fe-B master alloy that is purchased Hongwei Boron Alloy Co., Ltd., Donggang City production is 78.61% Fe+20.76% B+0.35% Si+ impurity (0.108% Al+0.018% P+0.15% C+0.004% S).
Embodiment 1
Take by weighing Fe-Ce-Si-Ca master alloy 1000 grams that are purchased and Fe-B master alloy 100 grams that are purchased, they are broken into fritter, put into the water jacketed copper crucible of vacuum quick quenching furnace, regulate electrode position, make it and crucible in the raw alloy particle between distance be 0.5mm, close fire door, feed inlet and outlet and purging valve, be evacuated to and be higher than 5 * 10
-3Behind the Pa, use ar purging, charge into argon gas subsequently to 0.04Pa, regulate arc current after the starting the arc and progressively rise to 500A, raw alloy in the crucible is melted, when treating that this alloy all is fused into liquid state, this crucible that tilts makes this alloy liquid cause on the water-cooled molybdenum wheel of high speed rotating by runner, molybdenum wheel edge line speed is 30m/ second, the molybdenum wheel surface is that temperature is 10 ℃, and this alloy liquid is with after this molybdenum wheel contact, solidifies rapidly and form thin ribbon shaped to take turns tangential direction along molybdenum and fly out, after stopping, baffle plate falls into the boxroom of body of heater bottom, it is 0.45mm that fast quenching obtains mean thickness, and width average is 0.65mm, and mean length is 1.35mm, crystal grain is designated hereinafter simply as nucleating agent 1 of the present invention less than the high-chromium cast iron composite inoculant of laminar nanocrystalline rare earth ferrosilicon+ferro-boron of 100nm.
Embodiment 2
Take by weighing Fe-Ce-Si-Ca master alloy 1200 grams that are purchased with embodiment 1 and Fe-B master alloy 84 grams that are purchased, they are broken into fritter, put into the water jacketed copper crucible of vacuum quick quenching furnace, regulate electrode position, make it and crucible in the raw alloy particle between distance be 1.0mm, close fire door, feed inlet and outlet and purging valve, be evacuated to and be higher than 5 * 10
-3Behind the Pa, use ar purging, charge into argon gas subsequently to 0.045Pa, regulate arc current after the starting the arc and progressively rise to 550A, raw alloy in the crucible is melted, when treating that this alloy all is fused into liquid state, this crucible that tilts makes this alloy liquid cause on the water-cooled molybdenum wheel of high speed rotating by runner, molybdenum wheel edge line speed is 35m/ second, molybdenum wheel surface temperature is 12.5 ℃, and this alloy liquid is with after this molybdenum wheel contact, solidifies rapidly and form thin ribbon shaped to take turns tangential direction along molybdenum and fly out, after stopping, baffle plate falls into the boxroom of body of heater bottom, it is 0.5mm that fast quenching obtains mean thickness, and width average is 0.7mm, and mean length is 1.5mm, crystal grain is designated hereinafter simply as nucleating agent 2 of the present invention less than the high-chromium cast iron composite inoculant of laminar nanocrystalline rare earth ferrosilicon+ferro-boron of 100nm.
Embodiment 3
Take by weighing Fe-Ce-Si-Ca master alloy 1100 grams that are purchased with embodiment 1 and Fe-B master alloy 143 grams that are purchased, they are broken into fritter, put into the water jacketed copper crucible of vacuum quick quenching furnace, regulate electrode position, make it and crucible in the raw alloy particle between distance be 1.5mm, close fire door, feed inlet and outlet and purging valve, be evacuated to and be higher than 5 * 10
-3Behind the Pa, use ar purging, charge into argon gas subsequently to 0.05Pa, regulate arc current after the starting the arc and progressively rise to 600A, raw alloy in the crucible is melted, when treating that this alloy all is fused into liquid state, this crucible that tilts makes this alloy liquid cause on the water-cooled molybdenum wheel of high speed rotating by runner, molybdenum wheel edge line speed is 40m/ second, molybdenum wheel surface temperature is 15 ℃, and this alloy liquid is with after this molybdenum wheel contact, solidifies rapidly and form thin ribbon shaped to take turns tangential direction along molybdenum and fly out, after stopping, baffle plate falls into the boxroom of body of heater bottom, it is 0.2mm that fast quenching obtains mean thickness, and width average is 0.3mm, and mean length is 0.8mm, crystal grain is designated hereinafter simply as nucleating agent 3 of the present invention less than the high-chromium cast iron composite inoculant of laminar nanocrystalline rare earth ferrosilicon+ferro-boron of 100nm.
Fig. 1 is the metallograph that is purchased the Fe-B master alloy of three peak rare earth company limiteds of Baogang production.Fig. 2 is the metallograph that is purchased the Fe-Ce-Si-Ca master alloy of Hongwei Boron Alloy Co., Ltd., Donggang City production.Fig. 3 is the transmission electron microscope displaing micro tissue topography of the prepared high-chromium cast iron composite inoculant of the present invention of embodiment 1,2 and 3.Fig. 1 is purchased the grain-size of ferro-boron in the Fe-B master alloy as can be known on average at 100 μ m; Be purchased the thick Fe-Si eutectic structure that exists in the rare earth ferrosilicon of Fe-Ce-Si-Ca master alloy greater than 200 μ m as shown in Figure 2; As shown in Figure 3, the grain-size of high-chromium cast iron composite inoculant of the present invention has reached nano level, because nano grain surface has high surface energy, so the nanometer nucleating agent can significantly reduce the critical forming core merit of the heterogeneous forming core of high-chromium cast iron alloy melt, improve the nucleation rate of high-chromium cast iron alloy melt, thereby overcome the casting flaw of high-chromium cast iron alloy, the matrix grain of high-chromium cast iron alloy is able to remarkable refinement mutually with cementite, thereby has improved the comprehensive mechanical property of high-chromium cast iron alloy significantly.
Routine embodiment 4～6 has disclosed the metal melting casting that high-chromium cast iron composite inoculant of the present invention is used for the high-chromium cast iron alloy tissue is carried out crystal grain and structure refinement processing down, wherein used batching first is the raw material of preparation rich chromium cast iron, and its chemical ingredients is that C=2.4～3.2%, Si≤1.2%, Mn≤1.2%, P≤0.05%, S≤0.05%, Cr=13～20%, Ni≤0.25%, V≤0.07%, B≤0.005% and all the other are Fe; Used batching second then is the high-chromium cast iron composite inoculant by the embodiment of the invention 1,2 or the 3 laminar nanocrystalline rare earth ferrosilicon+ferro-borons that prepare that specified sealing is preserved, nucleating agent 1,2 or 3 promptly of the present invention.
Down among the comparative example of routine embodiment 4～6 used batching second be with elementary composition be 30.7% Fe+30%Ce+37.5% Si+1.8% Ca be purchased Fe-Ce-Si-Ca master alloy that three peak rare earth company limiteds of Baogang produce and elementary composition be the high-chromium cast iron composite inoculant that the Fe-B master alloy that is purchased Hongwei Boron Alloy Co., Ltd., Donggang City production of 78.61% Fe+20.76%B+0.35%Si+ impurity (0.108% Al+0.018%P+0.15%C+0.004%S) makes by known traditional method, be designated hereinafter simply as traditional nucleating agent.
Embodiment 4
The first step, batching
Batching second is the nucleating agent of the present invention 1 that embodiment 1 makes,
By weight being the batching first: batching second=take by weighing batching at 100: 0.06, guarantee all material drying in the operating process;
Second step, the fusing of high-chromium cast iron alloy and refining
Batching first in the first step is put into Medium Frequency Induction Heating Furnace crucible internal heating to 1480 ℃, to the whole fusings of the first of preparing burden, the zinc chloride that is incorporated as batching first weight 2% carries out the degasification refining, removes gas and impurity in the batching first alloy melt, makes the high-chromium cast iron alloy melt after the refining;
The 3rd step, refinement
Under the condition of the temperature of fusion in second step, add the batching second that by the first step takes by weighing in the high-chromium cast iron alloy melt after second goes on foot the refining that makes in insulation, left standstill 4 seconds after mechanical stirring is even, make the refining high-chromium cast iron alloy melt after breeding;
The 4th step, casting
By the 3rd the step make breed after refining high-chromium cast iron alloy melt leave standstill cooling, after being controlled at 1390 ℃ to pouring temperature, refining high-chromium cast iron alloy melt after this is bred is cast in the sand mold mould, place the impurity that filtering net is carried secretly with removing during casting on the mould, treat molding behind this high-chromium cast iron alloy melt solidifying, obtain the high-chromium cast iron alloy foundry goods;
The 5th step, thermal treatment
The high-chromium cast iron alloy foundry goods that the casting of the 4th step is obtained is incubated 2 hours under temperature is 960 ± 10 ℃, handle through oil cooling, reheat to 300 ℃ carries out Shot Blasting and makes casting high-chromium cast iron alloy product, i.e. 1B in the category-B sample in the table 1 after the tempered processing.
The comparative example of embodiment 4
Remove the high-chromium cast iron composite inoculant of second of preparing burden for using Fe-Ce-Si-Ca master alloy 1000 grams that are purchased the production of three peak rare earth company limiteds of Baogang and Fe-B master alloy 100 grams that are purchased Hongwei Boron Alloy Co., Ltd., Donggang City production to make by known traditional method, be outside traditional nucleating agent 1, with other raw materials and technology all with embodiment 4, make casting high-chromium cast iron alloy product sample, i.e. 1A in the category-A sample in the table 1.
The metallographic structure contrast figure of high-chromium cast iron composite inoculant that Fig. 4 makes with traditional method for present embodiment and the high-chromium cast iron alloy product sample that under casting condition of the same race, makes with nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that the inventive method makes.Wherein scheme High Cr Cast Iron sample (the sample title: metallographic structure figure 1A-1#) that (a) makes for the composite inoculant that makes with traditional method; (b) High Cr Cast Iron sample (the sample title: metallographic structure figure 1B-1#) that makes for the nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that makes with the inventive method.Two kinds of as cast condition (be expressed as-1#) rich chromium cast iron sample tissue is compared as follows:
(a) (b)
Sample title: 1A-1# (rising head) sample title: 1B-1# (rising head)
Technology: casting (traditional nucleating agent 1 refinement) technology: casting (nucleating agent 1 refinement of the present invention)
Tissue: A transmutation product+eutectic carbides tissue: A transmutation product+eutectic carbides
Matrix relative quantity: 76.58% matrix relative quantity: 81.76%
Dendrite interval: 59.30 μ m dendrite intervals: 24.62 μ m
Magnification: 200X magnification: 200X
Etchant: 5% nital: 5% nitric acid alcohol
The rich chromium cast iron as-cast structure of above-mentioned two kinds of nucleating agent modifying-refinings is: A transmutation product+eutectic carbides, wherein A represents austenite.(down together)
Fig. 5 is high-chromium cast iron composite inoculant that makes with traditional method in the present embodiment and the rich chromium cast iron sample metallographic structure contrast figure of nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant under casting condition of the same race and same casting postheat treatment condition that makes with the inventive method.Wherein scheme heat treatment state rich chromium cast iron sample (the sample title: metallographic structure figure 1A-2#) that (a) makes for the composite inoculant that makes with traditional method; (b) heat treatment state rich chromium cast iron sample (the sample title: metallographic structure figure 1B-2#) that makes for the rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant of the nanometer product that make with the inventive method.Two kinds of heat treatment state (be expressed as-2#) rich chromium cast iron sample tissue is compared as follows:
(a) (b)
Sample title: 1A-2# (rising head) sample title: 1B-2# (rising head)
Technology: casting postheat treatment (traditional nucleating agent 1 refinement) technology: casting postheat treatment (nucleating agent 1 refinement of the present invention)
Tissue: M
Return+ A '+C
Altogether+ C
SecondaryTissue: M
Return+ A '+C
Altogether+ C
Secondary
Matrix relative quantity: 75.98% matrix relative quantity: 80.53%
Dendrite interval: 46.27 μ m dendrite intervals: 24.94 μ m
Magnification: 200X magnification: 200X
Etchant: 5% nital: 5% nitric acid alcohol
The tissue of the rich chromium cast iron casting heat treated (quenching+tempering) of above-mentioned two kinds of nucleating agent modifying-refinings is:
M
Return+ A '+C
Altogether+ C
Secondary, M wherein
ReturnBe tempered martensite, A ' is a residual austenite, C
AltogetherBe eutectic carbides, C
SecondaryBe proeutectoid carbide.(down together)
Embodiment 5
The first step, batching
Batching second is the nucleating agent of the present invention 2 that embodiment 2 makes,
By weight being the batching first: batching second=take by weighing batching at 100: 0.07, guarantee all material drying in the operating process;
Second step, the fusing of high-chromium cast iron alloy and refining
Batching first in the first step is put into Medium Frequency Induction Heating Furnace crucible internal heating to 1500 ℃, to the whole fusings of the first of preparing burden, add 2.5% zinc chloride and carry out the degasification refining, remove gas and impurity in the batching first alloy melt, make the high-chromium cast iron alloy melt after the refining;
The 3rd step, refinement
Under the condition of the temperature of fusion in second step, add the batching second that by the first step takes by weighing in the high-chromium cast iron alloy melt after second goes on foot the refining that makes in insulation, left standstill 5 seconds after mechanical stirring is even, make the refining high-chromium cast iron alloy melt after breeding;
The 4th step, casting
By the 3rd the step make breed after refining high-chromium cast iron alloy melt leave standstill cooling, after being controlled at 1400 ℃ to pouring temperature, refining high-chromium cast iron alloy melt after this is bred is cast in the sand mold mould, place the impurity that filtering net is carried secretly with removing during casting on the mould, treat molding behind this high-chromium cast iron alloy melt solidifying, obtain the high-chromium cast iron alloy foundry goods;
The 5th step, thermal treatment
The high-chromium cast iron alloy foundry goods that the casting of the 4th step is obtained is incubated 4 hours under temperature is 960 ± 10 ℃, handle through oil cooling, reheat to 300 ℃ carries out Shot Blasting and makes casting high-chromium cast iron alloy product, i.e. 2B in the category-B sample in the table 1 after the tempered processing.
The comparative example of embodiment 5
Remove the high-chromium cast iron composite inoculant of second of preparing burden for using Fe-Ce-Si-Ca master alloy 1200 grams that are purchased the production of three peak rare earth company limiteds of Baogang and Fe-B master alloy 84 grams that are purchased Hongwei Boron Alloy Co., Ltd., Donggang City production to make by known traditional method, be outside traditional nucleating agent 2, with other raw materials and technology all with embodiment 5, make casting high-chromium cast iron alloy product sample, i.e. 2A in the category-A sample in the table 1.
The metallographic structure contrast figure of the high-chromium cast iron alloy product sample that Fig. 6 makes under casting condition of the same race for the high-chromium cast iron composite inoculant that makes with traditional method in the present embodiment with nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that the inventive method makes.Wherein scheme High Cr Cast Iron sample (the sample title: metallographic structure figure 2A-1#) that (a) makes for the composite inoculant that makes with traditional method; (b) High Cr Cast Iron sample (the sample title: metallographic structure figure 2B-1#) that makes for the nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that makes with the inventive method.Two kinds of as cast condition (be expressed as-1#) rich chromium cast iron sample tissue is compared as follows:
(a) (b)
Sample title: 2A-1# (rising head) sample title: 2B-1# (rising head)
Technology: casting (traditional nucleating agent 2 refinements) technology: casting (nucleating agent 2 refinements of the present invention)
Tissue: A transmutation product+eutectic carbides tissue: A transmutation product+eutectic carbides
Matrix relative quantity: 74.52% matrix relative quantity: 82.65%
Dendrite interval: 52.24 μ m dendrite intervals: 21.22 μ m
Magnification: 200X magnification: 200X
Etchant: 5% nital: 5% nitric acid
Fig. 7 is high-chromium cast iron composite inoculant that makes with traditional method in the present embodiment and the rich chromium cast iron sample metallographic structure contrast figure of nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant under casting condition of the same race and same casting postheat treatment condition that makes with the inventive method.Wherein scheme heat treatment state rich chromium cast iron sample (the sample title: metallographic structure figure 2A-2#) that (a) makes for the composite inoculant that makes with traditional method; (b) heat treatment state rich chromium cast iron sample (the sample title: metallographic structure figure 2B-2#) that makes for the nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that makes with the inventive method.Two kinds of heat treatment state (be expressed as-2#) rich chromium cast iron sample tissue is compared as follows:
(a) (b)
Sample title: 2A-2# (rising head) sample title: 2B-2# (rising head)
Technology: casting postheat treatment (traditional nucleating agent 2 refinements) technology: casting postheat treatment (nucleating agent 2 refinements of the present invention)
Tissue: M
Return+ A '+C
Altogether+ C
SecondaryTissue: M
Return+ A '+C
Altogether+ C
Secondary
Matrix relative quantity: 77.27% matrix relative quantity: 83.07%
Dendrite interval: 67.52 μ m dendrite intervals: 24.25 μ m
Magnification: 200X magnification: 200X
Etchant: 5% nital: 5% nitric acid alcohol
Embodiment 6
The first step, batching
Batching second is the high-chromium cast iron composite inoculant of embodiment 3 preparations, nucleating agent 3 promptly of the present invention,
By weight being the batching first: batching second=take by weighing batching at 100: 0.08, guarantee all material drying in the operating process;
Second step, the fusing of high-chromium cast iron alloy and refining
Batching first in the first step is put into Medium Frequency Induction Heating Furnace crucible internal heating to 1550 ℃, to the whole fusings of the first of preparing burden, add 3% zinc chloride and carry out the degasification refining, remove gas and impurity in the batching first alloy melt, make the high-chromium cast iron alloy melt after the refining;
The 3rd step, refinement
Under the condition of the temperature of fusion in second step, add the batching second that by the first step takes by weighing in the high-chromium cast iron alloy melt after second goes on foot the refining that makes in insulation, left standstill 6 seconds after mechanical stirring is even, make the refining high-chromium cast iron alloy melt after breeding;
The 4th step, casting
By the 3rd the step make breed after refining high-chromium cast iron alloy melt leave standstill cooling, after being controlled at 1430 ℃ to pouring temperature, refining high-chromium cast iron alloy melt after this is bred is cast in the sand mold mould, place the impurity that filtering net is carried secretly with removing during casting on the mould, treat molding behind this high-chromium cast iron alloy melt solidifying, obtain the high-chromium cast iron alloy foundry goods;
The 5th step, thermal treatment
The high-chromium cast iron alloy foundry goods that the casting of the 4th step is obtained is incubated 5 hours under temperature is 960 ± 10 ℃, handle through oil cooling, reheat to 300 ℃, carry out after the tempered processing Shot Blasting make the casting high-chromium cast iron alloy produce brilliant, i.e. 3B in the category-B sample in the table 1.
The comparative example of embodiment 6
Remove the high-chromium cast iron composite inoculant of second of preparing burden for using Fe-Ce-Si-Ca master alloy 1100 grams that are purchased the production of three peak rare earth company limiteds of Baogang and Fe-B master alloy 143 grams that are purchased Hongwei Boron Alloy Co., Ltd., Donggang City production to make by known traditional method, be outside traditional nucleating agent 3, with other raw materials and technology all with embodiment 6, make casting high-chromium cast iron alloy product sample, i.e. 3A in the category-A sample in the table 1.
The metallographic structure contrast figure of the high-chromium cast iron alloy product sample that Fig. 8 makes under casting condition of the same race for the high-chromium cast iron composite inoculant that makes with traditional method in the present embodiment with nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that the inventive method makes.Wherein scheme High Cr Cast Iron sample (the sample title: metallographic structure figure 3A-1#) that (a) makes for the composite inoculant that makes with traditional method; (b) High Cr Cast Iron sample (the sample title: metallographic structure figure 3B-1#) that makes for the nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that makes with the inventive method.Two kinds of as cast condition (be expressed as-1#) rich chromium cast iron sample tissue is compared as follows:
(a) (b)
Sample title: 3A-1# (rising head) sample title: 3B-1# (rising head)
Technology: casting (traditional nucleating agent 3 refinements) technology: casting (nucleating agent 3 refinements of the present invention)
Tissue: A transmutation product+eutectic carbides tissue: A transmutation product+eutectic carbides
Matrix relative quantity: 71.38% matrix relative quantity: 80.02%
Dendrite interval: 43.27 μ m dendrite intervals: 23.96 μ m
Magnification: 200X magnification: 200X
Etchant: 5% nital: 5% nitric acid alcohol
Fig. 9 is high-chromium cast iron composite inoculant that makes with traditional method in the present embodiment and the rich chromium cast iron sample metallographic structure contrast figure of nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant under casting condition of the same race and same casting postheat treatment condition that makes with the inventive method.Wherein scheme heat treatment state rich chromium cast iron sample (the sample title: metallographic structure figure 3A-2#) that (a) makes for the composite inoculant that makes with traditional method; (b) heat treatment state rich chromium cast iron sample (the sample title: metallographic structure figure 3B-2#) that makes for the nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that makes with the inventive method.Two kinds of heat treatment state (be expressed as-2#) rich chromium cast iron sample tissue is compared as follows:
(a) (b)
Sample title: 3A-2# (rising head) sample title: 3B-2# (rising head)
Technology: casting postheat treatment (traditional nucleating agent 3 refinements) technology: casting postheat treatment (nucleating agent 3 refinements of the present invention)
Tissue: M
Return+ A '+C
Altogether+ C
SecondaryTissue: M
Return+ A '+C
Altogether+ C
Secondary
Matrix relative quantity: 77.74% matrix relative quantity: 83.46%
Dendrite interval: 51.70 μ m dendrite intervals: 24.13 μ m
Magnification: 200X magnification: 200X
Etchant: 5% nital: 5% nitric acid alcohol
Figure 10 is high-chromium cast iron composite inoculant that makes with traditional method in the present embodiment and the nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant eutectic carbides interlamellar spacing contrast figure in casting condition of the same race and the same rich chromium cast iron sample metallographic structure ledeburite of casting under the postheat treatment condition that makes with the inventive method.Wherein scheme heat treatment state rich chromium cast iron sample (the sample title: metallographic structure figure 3A-2#) that (a) makes for the composite inoculant that makes with traditional method; (b) heat treatment state rich chromium cast iron sample (the sample title: metallographic structure figure 3B-2#) that makes for the nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant that makes with the inventive method.Two kinds of heat treatment state (be expressed as-2#) rich chromium cast iron sample tissue is compared as follows:
(a) (b)
Sample title: 3A-2# (rising head) sample title: 3B-2# (rising head)
Technology: casting postheat treatment (traditional nucleating agent 3 refinements) technology: casting postheat treatment (nucleating agent 3 refinements of the present invention)
Tissue: M
Return+ A '+C
Altogether+ C
SecondaryTissue: M
Return+ A '+C
Altogether+ C
Secondary
Matrix relative quantity: 77.74% matrix relative quantity: 83.46%
Dendrite interval: 51.70 μ m dendrite intervals: 24.13 μ m
Eutectic carbides interlamellar spacing 9.80 μ m eutectic carbides interlamellar spacings 4.0 μ m
Magnification: 500X magnification: 500X
Etchant: 5% nital: 5% nitric acid alcohol
Embodiment 7
The first step, batching
Batching second is the high-chromium cast iron composite inoculant of embodiment 3 preparations, nucleating agent 3 promptly of the present invention,
By weight being the batching first: batching second=take by weighing batching at 100: 0.04, guarantee all material drying in the operating process;
Second step, the fusing of high-chromium cast iron alloy and refining
Batching first in the first step is put into Medium Frequency Induction Heating Furnace crucible internal heating to 1520 ℃, to the whole fusings of the first of preparing burden, add 3% zinc chloride and carry out the degasification refining, remove gas and impurity in the batching first alloy melt, make the high-chromium cast iron alloy melt after the refining;
The 3rd step, refinement
Under the condition of the temperature of fusion in second step, add the batching second that by the first step takes by weighing in the high-chromium cast iron alloy melt after second goes on foot the refining that makes in insulation, left standstill 6 seconds after mechanical stirring is even, make the refining high-chromium cast iron alloy melt after breeding;
The 4th step, casting
By the 3rd the step make breed after refining high-chromium cast iron alloy melt leave standstill cooling, after being controlled at 1410 ℃ to pouring temperature, refining high-chromium cast iron alloy melt after this is bred is cast in the sand mold mould, place the impurity that filtering net is carried secretly with removing during casting on the mould, treat molding behind this high-chromium cast iron alloy melt solidifying, obtain the high-chromium cast iron alloy foundry goods;
The 5th step, thermal treatment
The high-chromium cast iron alloy foundry goods that the casting of the 4th step is obtained is incubated 3 hours under temperature is 960 ± 10 ℃, handle through oil cooling, reheat to 300 ℃ carries out Shot Blasting and makes casting high-chromium cast iron alloy product, i.e. 4B in the category-B sample in the table 1 after the tempered processing.
The comparative example of embodiment 7
Remove the high-chromium cast iron composite inoculant that batching second makes by known traditional method for Fe-B master alloy 143 grams that use Fe-Ce-Si-Ca master alloy 1100 grams that are purchased the production of three peak rare earth company limiteds of Baogang and the Hongwei Boron Alloy Co., Ltd., Donggang City that is purchased to produce, be outside traditional nucleating agent 3, with other raw materials and technology all with embodiment 7, make casting high-chromium cast iron alloy product sample, i.e. 4A in the category-A sample in the table 1.
Percentage ratio in the foregoing description is weight percentage, and oil cooling processing, temper and the Shot Blasting in the foregoing description all is known processing methodes.
In the foregoing description 4～7, the said high-chromium cast iron alloy product that makes of the 5th step is engineering machinery high chrome cast iron lining plate wearing piece and a mechanical property standard test specimen thereof.
Distinguish the A of refinement, the basic mechanical performance testing mean result of B two class rich chromium cast iron samples with traditional nucleating agent and nucleating agent of the present invention among table 1 embodiment 4～7
Data in the comparison sheet 1 as can be known, breed the rich chromium cast iron sample (being above-mentioned category-A sample) of refinement compares with traditional nucleating agent, the tensile strength of the rich chromium cast iron sample after breeding refinement with nucleating agent of the present invention (being above-mentioned category-B sample) is significantly improved, and the toughness of rich chromium cast iron and Young's modulus also slightly improve.The comprehensive mechanical property that experimental results show that above-mentioned category-B sample obviously is better than above-mentioned category-A sample.
As everyone knows, the height of material property depends on the excellent summary of its microtexture.Difference for the refining effect of better nanocrystalline rare earth ferrosilicon+ferro-boron high-chromium cast iron composite inoculant more of the present invention and traditional rare earth ferrosilicon+ferro-boron nucleating agent, we by two kinds of metallographicobservation comparative analyses breed fining agent to the rich chromium cast iron as cast condition of mentioned component and thermal treatment after the influence of microstructure, metallographicobservation detected result such as Fig. 4 are to shown in Figure 9.
From the paired observation of metallographic structure A, the B of Fig. 4 to Fig. 9 group as can be seen: among three groups of contrast rich chromium cast iron as-cast structure figure (being Fig. 4, Fig. 6 and Fig. 8), nucleating agent of the present invention to the thinning effect of A transmutation product+eutectic carbides all clearly; In three groups of contrast casting postheat treatment organization charts (being Fig. 5, Fig. 7 and Fig. 9), nucleating agent of the present invention is to M
Return+ A '+C
Altogether+ C
SecondaryThinning effect all clearly.Found out eutectic carbides interlamellar spacing in the rich chromium cast iron sample metallographic structure ledeburite of casting condition of the same race by Figure 10: (a) that traditional nucleating agent refinement is 9.8 μ m; That (b) nucleating agent of the present invention breeds refinement is 4 μ m.Therefore can draw nanocrystalline rare earth ferrosilicon of the present invention+ferro-boron high-chromium cast iron composite inoculant has special advantages aspect the microstructure after breeding refinement rich chromium cast iron as cast condition and thermal treatment.
Claims (5)
1. high-chromium cast iron composite inoculant, it is characterized in that: it is a kind of high-chromium cast iron composite inoculant of nanocrystalline rare earth ferrosilicon+ferro-boron, form by Fe-Ce-Si-Ca master alloy and Fe-B master alloy, wherein, the elementary composition of Fe-Ce-Si-Ca master alloy is 30.7%Fe+30%Ce+37.5%8i+1.8%Ca, the elementary composition of Fe-B master alloy is 78.61%Fe+20.76%B+0.35%Si+ impurity, this impurity is 0.108%Al+0.018%P+0.15%C+0.004%S, the weight ratio of these two kinds of master alloys is the Fe-Ce-Si-Ca master alloy: Fe-B master alloy=1: 0.07～0.13, the nanocrystalline crystal grain of this nucleating agent is less than 100nm.
2. high-chromium cast iron composite inoculant according to claim 1, it is characterized in that: it is a kind of high-chromium cast iron composite inoculant of laminar nanocrystalline rare earth ferrosilicon+ferro-boron, the mean thickness of this thin slice is 0.2～0.5mm, width average is 0.3～0.7mm, and mean length is 0.8～1.5mm.
3. the preparation method of high-chromium cast iron composite inoculant, it is characterized in that: be that a kind of centrifugal fast quenching gets rid of the band method, concrete steps are: with elementary composition be 30.7%Fe+30%Ce+37.5%Si+1.8%Ca be purchased the Fe-Ce-Si-Ca master alloy and the elementary composition Fe-B master alloy that is purchased for 78.61%Fe+20.76%B+0.35%Si+ impurity is a raw material, above-mentioned impurity is 0.108%Al+0.018%P+0.15%C+0.004%S, it is the Fe-Ce-Si-Ca master alloy by weight: Fe-B master alloy=1: 0.07～0.13, take by weighing the Fe-Ce-Si-Ca master alloy that is purchased of aequum and the Fe-B master alloy that is purchased, put into the water jacketed copper crucible of vacuum quick quenching furnace, regulate electrode position, make it and crucible in the raw alloy particle between distance be 0.5～1.5mm, close fire door, feed inlet and outlet and purging valve are evacuated to and are higher than 5 * 10
-3Behind the Pa, use ar purging, charge into argon gas to 0.04～0.05Pa subsequently, regulate arc current after the starting the arc and progressively rise to 500～600A, raw alloy in the crucible is melted, when treating that this alloy all is fused into liquid state, this crucible that tilts makes this alloy liquid cause on the water-cooled molybdenum wheel of high speed rotating by runner, molybdenum wheel edge line speed is 30～40m/ second, molybdenum wheel surface temperature is 10～15 ℃, this alloy liquid is with after this molybdenum wheel contact, solidifies rapidly and form thin ribbon shaped to take turns tangential direction along molybdenum and fly out, and falls into the boxroom of body of heater bottom after baffle plate stops, it is 0.2～0.5mm that fast quenching obtains mean thickness, width average is 0.3～0.7mm, and mean length is 0.8～1.5mm, and crystal grain is less than the high-chromium cast iron composite inoculant of laminar nanocrystalline rare earth ferrosilicon+ferro-boron of 100nm.
4. the application of the described high-chromium cast iron composite inoculant of claim 2 is to use it for the high-chromium cast iron alloy tissue is carried out crystal grain and structure refinement processing, and treatment process is the metal melting casting, it is characterized in that concrete steps are as follows:
The first step, batching
The batching first is the raw material of preparation rich chromium cast iron, and its chemical ingredients is that C=2.4～3.2%, Si≤1.2%, Mn≤1.2%, P≤0.05%, S≤0.05%, Cr=13～20%, Ni≤0.25%, V≤0.07%, B≤0.005% and all the other are Fe,
The high-chromium cast iron composite inoculant of the described laminar nanocrystalline rare earth ferrosilicon+ferro-boron of the claim 2 that batching second is preserved for sealing,
By weight being the batching first: batching second=100: 0.04～0.08 takes by weighing batching, guarantees all material drying in the operating process;
Second step, the fusing of high-chromium cast iron alloy and refining
Batching first in the first step is put into Medium Frequency Induction Heating Furnace crucible internal heating to 1480～1550 ℃, to the whole fusings of the first of preparing burden, the zinc chloride that is incorporated as batching first weight 2～3% carries out the degasification refining, remove gas and impurity in the batching first alloy melt, make the high-chromium cast iron alloy melt after the refining;
The 3rd step, refinement
Under the condition of the temperature of fusion in second step, add the batching second that by the first step takes by weighing in the high-chromium cast iron alloy melt after second goes on foot the refining that makes in insulation, left standstill 4～6 seconds after mechanical stirring is even, make the refining high-chromium cast iron alloy melt after breeding;
The 4th step, casting
With the 3rd the step make breed after refining high-chromium cast iron alloy melt leave standstill cooling, after being controlled at 1390～1430 ℃ to pouring temperature, refining high-chromium cast iron alloy melt after again this being bred is cast in the sand mold mould, place the impurity that filtering net is carried secretly with removing during casting on the mould, treat molding behind the high-chromium cast iron alloy melt solidifying, obtain the high-chromium cast iron alloy foundry goods;
The 5th step, thermal treatment
The high-chromium cast iron alloy foundry goods that the 4th step casting is obtained is 960 ± 10 ℃ of insulations 2～5 hours down in temperature, handles through oil cooling, and reheat to 300 ℃ carries out Shot Blasting and makes casting high-chromium cast iron alloy product after the tempered processing.
Percentage ratio in the aforesaid method is weight percentage, and oil cooling processing, temper and the Shot Blasting in the aforesaid method all is known processing methodes.
5. the application of the described high-chromium cast iron composite inoculant of the described claim 2 of claim 4 is characterized in that: wherein the said high-chromium cast iron alloy product that makes of the 5th step is engineering machinery high chrome cast iron lining plate wearing piece and a mechanical property standard test specimen thereof.
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| CN102181779B (en) * | 2011-04-01 | 2012-11-07 | 河北工业大学 | Composite inoculant used for grey cast iron and preparation method and application method of composite inoculant |
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| CN106435335B (en) * | 2016-11-17 | 2018-03-30 | 石卫东 | Amorphous inovulant for rich chromium cast iron and preparation method thereof and application method |
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| CN110438392B (en) * | 2019-08-20 | 2020-09-01 | 新沂永新机械配件有限公司 | Nitrogen-containing compound inoculant for greatly improving cast iron performance |
| CN113278756A (en) * | 2021-04-19 | 2021-08-20 | 成都宏源铸造材料有限公司 | Preparation method of silicon inoculant for cast iron |
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