CN104812922A - Inoculant alloy for thick cast-iron parts - Google Patents
Inoculant alloy for thick cast-iron parts Download PDFInfo
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- CN104812922A CN104812922A CN201380059199.9A CN201380059199A CN104812922A CN 104812922 A CN104812922 A CN 104812922A CN 201380059199 A CN201380059199 A CN 201380059199A CN 104812922 A CN104812922 A CN 104812922A
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- alloy
- antimony
- inoculant alloy
- cast iron
- inoculant
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 103
- 239000000956 alloy Substances 0.000 title claims abstract description 103
- 229910001018 Cast iron Inorganic materials 0.000 title claims abstract description 66
- 239000002054 inoculum Substances 0.000 title claims abstract description 63
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 70
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims abstract description 7
- 239000002667 nucleating agent Substances 0.000 claims description 47
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 27
- 239000011777 magnesium Substances 0.000 claims description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 42
- 239000010439 graphite Substances 0.000 description 32
- 229910002804 graphite Inorganic materials 0.000 description 32
- 238000000034 method Methods 0.000 description 32
- 238000005266 casting Methods 0.000 description 25
- 238000011081 inoculation Methods 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 18
- 239000011575 calcium Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 238000009826 distribution Methods 0.000 description 14
- 229910052791 calcium Inorganic materials 0.000 description 13
- 230000007547 defect Effects 0.000 description 13
- 229910052797 bismuth Inorganic materials 0.000 description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000006698 induction Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000011435 rock Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 229910001567 cementite Inorganic materials 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000009395 breeding Methods 0.000 description 4
- 230000001488 breeding effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 229910005347 FeSi Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910001037 White iron Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 238000012809 post-inoculation Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910021346 calcium silicide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 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
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/10—Cast-iron alloys containing aluminium or silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D19/00—Casting in, on, or around objects which form part of the product
- B22D19/14—Casting in, on, or around objects which form part of the product the objects being filamentary or particulate in form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/20—Measures not previously mentioned for influencing the grain structure or texture; Selection of compositions therefor
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/08—Manufacture of cast-iron
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/10—Making spheroidal graphite cast-iron
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/10—Making spheroidal graphite cast-iron
- C21C1/105—Nodularising additive agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/18—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on silicides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0242—Making ferrous alloys by powder metallurgy using the impregnating technique
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0264—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/08—Making cast-iron alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention relates to an inoculant alloy for the treatment of thick cast-iron parts, based on ferrosilicon and containing between 0.005 and 3 weight percent of rare earths, and characterised in that it also contains between 0.2 and 2 weight percent of antimony.
Description
Technical field
The present invention relates to a kind of inoculant alloy for the treatment of cast iron.
Background technology
Cast iron is a kind of well-known iron-carbon, and it is widely used for manufacturing machine parts.Cast iron by before casting in a mold, at the temperature between 1320-1450 DEG C, is obtained by the alloy that cooling obtains with liquid state hybrid alloys composition.
When cooled, carbon can take several physicalchemical structure according to several parameter.
When carbon together with metal and formed iron carbide Fe
3time C (also referred to as cementite), the cast iron of acquisition is called white iron.White iron has hard and crisp character, and this is not satisfied for some application.
If carbon exists with the form of graphite, the cast iron of acquisition is called graphitic cast iron.Graphitic cast iron is softer and can be processed.
In order to obtain the cast iron member with good mechanical properties, be therefore necessary to obtain the structure of cast iron, this cast-iron structure comprises maximum quantity with the carbon of form of graphite, and limits these as far as possible and make alloy hardening and the formation of the iron carbide become fragile.
But without any in specific inoculation, carbon easily and iron combine thus form iron carbide.Therefore, be necessary to process cast iron in liquid state thus change the correlation parameter of carbon and obtain the structure expected.
For this reason, liquid cast is through inoculation, and the object of this inoculation is in cast iron, introduce greying composition or greying carrier, is commonly referred to core (germe), promotes graphite but not the appearance of iron carbide when cast iron cools by a mold.
Usually, the composition of nucleating agent is therefore by promoting that at cast iron setting up period the element of the decomposition of being formed of graphite and iron carbide is formed.Embodiment can comprise carbon, silicon, calcium, aluminium
Certainly, can nucleating agent be designed thus meet other functions and comprise other composition with special role for this reason.Cast iron also can through extra process before or subsequently.
Therefore, according to desired properties, especially expect that the graphite formed is spherical, vermiform or laminar.
Or graphite shape can preferably by the mode of special component by obtaining the special processing of cast iron.
Therefore, such as, by being called that the process of spheroidizing can promote the formation of globular graphite, spheroidizing main purpose is for cast iron provides enough magnesium, thus graphite can grow, to form circular granular (spherule or ore deposit knurl).
These nodulizing agent compositions added with the form of particular alloy (inoculant alloy) usually during particular procedure before the nucleating agent process of cast iron.
Therefore, inoculant alloy fundamentally can affect the shape of graphite spheroids, and wherein the object of inoculant products is the quantity of these spheroids of increase and makes graphite-structure homogenizing.
Can also mention and add desulfurization product or can according to the product of some defects of the initial composition particular procedure cast iron of liquid cast bath, these defects are such as the small shrinkage cavity or perforation that possible during cooling occur.
These process can implement one or many in the different moment during manufacture cast iron.
Major part nucleating agent is usually by ferro-silicon such as FeSi
45, FeSi
65or FeSi
75manufacture, simultaneously according to the nucleating agent composition adjustment chemical composition of target.Described nucleating agent also can be made up of the mixture of several alloy.
It should be noted, the inoculation efficiency of cast iron member also depends on its thickness (or depending on solidification rate).
In the region that thickness is little, cooling is faster, will note the risk of larger formation carbide.
On the contrary, in the region that thickness is larger, cooling is by slack-off (2-4 hour) and will promote the formation of graphite.
Therefore, the parts with different thickness region can have different physicalchemical structure from a region to another region, and this is less desirable.
In addition, the regional control crystal nucleation larger at thickness is still difficult, and can cause obtaining inconsistent structure.
For the parts had compared with heavy thickness, when not controlling inoculation method, the graphite of degeneration and/or the formation of " tubbiness " graphite may reduce the mechanical property of cast iron.In order to solve these defects, Metallurgical Factory adds star antimony usually in liquid metal.
In liquid metal, add star antimony, because the ratio very low (in liquid cast per ton the 10-30g order of magnitude) introduced, create accuracy problem.The interpolation efficiency of star antimony is between 50-80%, and effectively therefore introduction volume is difficult to control.
If amount not, can form the graphite of degeneration in the structure.
On the contrary, if introduction volume is greater than target, antimony will be easy to significantly increase perlitic ratio, and perlitic be less desirable in ferritic structure.
When adding star antimony, Metallurgical Factory should add rare earth element (being called for short RE) further thus obtain the maximum improvement of graphite shape.Similarly, if the quantity not sufficient of rare earth element, these parts will have " pointed " type graphite defect.On the contrary, if rare earth element amount is too high, graphite defect will be " short and thick " type, the type substantially appear at the starting material of use relatively pure time.
These " pointed " or " short and thick " type graphite defect worsen the mechanical property of cast iron, the tensile strength of the parts especially formed and shock resistance.
In addition, in liquid cast, introduce star antimony cause it to vaporize, and therefore cause strong venting.Measured, along with the interpolation of star antimony, the threshold value of the release of antimony is in the work environment higher than 0.5mg/m
3, this is release ultimate value (this ultimate value ELV is by regulation setting).Therefore, operator must have on the mouth mask work for protecting N95 type particulate or higher particulate.
The process of the parts with less thickness has been considered to be used for developing specific nucleating agent.Document FR2511044A1, FR2855186A1 and EP0816522A1 describe such nucleating agent for thin parts.
According to these documents, those nucleating agents for thin parts especially comprise ferrosilicon base inoculant alloy, and the rare earth element comprised by weight between 0.005-0.3%, especially lanthanum, and bismuth, lead or the antimony by weight between 0.005-0.3%, the ratio of the rare earth element had/(bismuth+lead+antimony) is between 0.9-2.2; Bismuth is particularly preferred, protects and only protect bismuth in the specification sheets of these documents.
It should be noted that these documents only disclose the purposes of antimony in general mode, and they do not comprise specific embodiment, also do not comprise the particular value about this element.
Be referred in the document of the purposes of antimony at other, following document can be enumerated.
Document WO2006/068487A1 describes a kind of nucleating agent, and it comprises phase altered contents (function of nucleating agent) and the reagent for modified graphite structure, and this reagent can be made up of antimony.It should be noted, this structurally-modified reagent is used for the mixture of nucleating agent compound (ferrosilicon), and is not the form of combining.In addition, it is pearl rock mass promotor that antimony is significantly taken as, and as mentioned above, this phase is normally less desirable.The usage quantity of antimony is between 3-15%, and the origin place that this usage quantity is equivalent to divide at the perlite body formed significantly measures.
Document JP2200718A describes a kind of nucleating agent, and it is made up of the mixture of ferrosilicon, antimony, calcium silicide and rare earth element.Antimony does not use with the form of associating.
Document JP57067146A describes silicon ferrous alloy, it comprise antimony by weight between 5-50% and up to 10% rare earth element.Except a high proportion of antimony, this alloy is used as pearl rock mass inhibitor, and is not used as nucleating agent.
Also have some articles and document to relate to the nodulizing agent function (form of graphite) of antimony, it is not main purpose and does not solve problems of inoculation (quality and quantity of ore deposit knurl).In addition, its generally include antimony with mixing and the purposes of the form of non-associating.
Therefore, a kind of inoculant alloy that can improve the process of thick parts is needed.
Summary of the invention
For this reason, target of the present invention is a kind of inoculant alloy for the treatment of thick ferrosilicon base cast iron member, described inoculant alloy comprises the rare earth element by weight between 0.005-3%, it is characterized in that, described inoculant alloy also comprises the antimony by weight between 0.2-2%.
Therefore, unexpected discovery really, when antimony ratio as requested combines rare earth element in silicon ferrous alloy, realization is effectively bred and has stable spherule by antimony, and these thick parts do not have the above-mentioned shortcoming mentioned of star antimony.
Especially, introduce antimony with the form of alloy and allow the effective use realizing antimony, the order of magnitude is 97-99%.Therefore, effective introduction volume is more accurately learnt.
Therefore, the raising of efficiency can be used in product economy and simplifies the management of product additive (comprising rare earth element).
Due to this efficiency increase and reduce gas purging in air simultaneously, for these additives of management operator Working environment also improve.
Use can limit antimony according to alloy of the present invention be emitted on 0.1-0.2mg/m
3between, and no longer need to use breathing mask.
Also it should be noted that the associating of antimony/rare earth element extends the fall time of antimony significantly.Therefore, the product effect lasts long period in whole castingprocesses.Will be noted that, in the inoculant alloy for thin parts, be even longer than the fall time of bismuth the fall time of antimony.
According to the alloy of the application after adding ladle or smelting furnace, can therefore, it is possible to replace and even cancel extra injection or with post inoculation.
Also strongly can limit especially according to the alloy of the application and even avoid " short and thick " or " pointed " type graphite defect, but also by determining that Oxygen potential is greater than 95% and impels spherule close to the perfect spherical form further improving graphite simultaneously.
Therefore, can guarantee the uniform ferrite/pearl rock mass matrix of the manufacture component of different thickness according to the alloy of the application, this especially improves the condition of parts with post-treatment.
Preferably, the ratio of antimony and rare earth element will higher than 1.4, preferably higher than 1.6, and lower than 2.5, preferably lower than 2.
According to the first changing conditions, inoculant alloy also comprises magnesium.So it will be the nodulizing agent with extra nucleating agent effect.
Unexpectedly, especially find different from the bismuth used, antimony can make the magnesium of introducing cast iron reach better efficiency.
For bismuth, known the latter accelerates pouring at Magnesium in Cast Iron, and because this latter loss is more for changing into the activated carbon of globular graphite by flake graphite.According to the present invention, can guarantee that remaining magnesium has good stability between 1350-1580 DEG C with the good assimilation of nodulizing agent form antimony.
According to the second changing conditions, inoculant alloy does not comprise magnesium.
Preferably, the ratio of rare earth element and antimony is between 0.9-2.2.
Preferably, the weight ratio of antimony higher than 0.3%, preferably higher than 0.5%, more preferably higher than 0.8%.
Preferably, the weight ratio of antimony lower than 1.5%, preferably lower than 1.3%.
Advantageously, rare earth element comprises lanthanum, preferably only has lanthanum.
Preferably, the weight ratio of rare earth element higher than 0.2%, preferably higher than 0.3%.
Preferably, the weight ratio of rare earth element lower than 1.2%, preferably lower than 1%.
The present invention also relates to the purposes according to nucleating agent of the present invention.
According to the first changing conditions of purposes, described nucleating agent is introduced in the form of a powder.
It should be noted, the defect of the product described in document FR2511044A1 and EP0816522A1 is between the nucleating agent shelf lives, and the size-grade distribution of product is demoted in time.The high stability of size-grade distribution in some conditions has been shown according to nucleating agent of the present invention.
According to the second changing conditions, described nucleating agent is introduced with the form of setting solid in the mould.
Preferably, according to the purposes of nucleating agent of the present invention, its objective is the cast iron member manufacturing and there is thickness and be greater than the part of 6mm, preferably there is the part that thickness is greater than 20mm, more preferably there is the part that thickness is greater than 50mm.
Embodiment
According to following description and embodiment, the present invention will better be understood.
Nucleating agent according to the present invention will be typically used in the situation of inoculated cast iron bath.If it also may be used for the pre-treatment or suitable for nodulizing agent of described cast iron.
When usually using nucleating agent, the composition according to inoculant alloy of the present invention can such as comprise:
| Element | Content (by weight %) |
| Si | 45–80 |
| Ca | 0.5–4 |
| Al | 0.5–3 |
| Sb | 0.2–2 |
| Rare earth element (comprising lanthanum) | 0.2–3 |
| Iron | Surplus |
Inoculant alloy-composition 1
Certainly, nucleating agent can also comprise extra element, and these elements bring concrete effect according to desired properties.More specifically, so same in the pretreated situation of cast iron.
Such as, therefore inoculant alloy can have following composition:
| Element | Content (by weight %) |
| Si | 45–80 |
| Ca | 0.5–8 |
| Al | 0.5–3 |
| Sb | 0.2–2 |
| Rare earth element (comprising lanthanum) | 0.2–3 |
| Ba | 2–15 |
| Mn | 2–6 |
| Zr | 2–6 |
| Iron | Surplus |
Inoculant alloy-composition 2
Inoculation adds the nucleating agent of 0.05 (preferably at least 0.1%)-0.8% by weight in cast-iron molten bath by usually comprising, especially in following setting as under the condition of embodiment:
-melt in induction furnace
-before use magnesium carries out spheroidizing, and more specifically, 1-5 minute before this treatment
-as the hovel of " sandwich " subsequently or " Tunsich-hovel " type process
-in foundry furnace
-between two ladles, shift (especially shift and cast) period
-pre-treatment nucleating agent can add and especially add with the form of powder cored filament material.
Size-grade distribution according to nucleating agent of the present invention can adjust according to its addition means.
Embodiment can comprise:
-to add in induction furnace: size-grade distribution is up to about 40mm.
-to add between induction furnace and casting pot: size-grade distribution is about between 30mm at about 10-.
-to add in casting basin: size-grade distribution is about between 2mm at about 0.4-.
-in castingin to mould before add: size-grade distribution is about 0.2 with about between 0.5-2mm.
-add with the form of setting nucleating agent in the mould: such as, 20g, 40g, 60g, 80g, 300g, 800g, 2kg, 5kg, 10kg, 20kg and 50kg inserts.
Inoculant alloy also successfully can add as nucleating agent or adjust the post inoculation of chemical composition (Ba is by weight between 1.5-5% particularly, and Ca is by weight between 0.5-2%) of alloy subsequently before being full of mold or during ladle.
According to the metallurgical state used according to the cast iron after the inoculant alloy process of the application, likely cancel the step after breeding.In fact, the effect of antimony is used to keep pregnant effect to be used for can significantly reducing the inoculation even cancelling the later stage for more time.Such as, when interpolation comprises the right nucleating agent of Bi/RE, pregnant effect loss 30% in initial 4 minutes.Therefore, in order to realize the pregnant effect of recovery 100%, the interpolation of later stage nucleating agent becomes enforceable.Not this situation according to the nucleating agent of the application.
When as when having the nodulizing agent of extra nucleating agent function, the composition of alloy also will comprise magnesium.Such as, such inoculant alloy composition with nucleating agent function can be as follows:
| Element | Content (% by weight) |
| Si | 30–60 |
| Ca | 0.2–5 |
| Al | 0.2–3 |
| Sb | 0.1–2 |
| Rare earth element (comprising lanthanum) | 0.1–3 |
| Mg | 3–12 |
| Iron | Surplus |
There is the inoculant alloy-composition 3 of nucleating agent effect
According to the size-grade distribution of nodulizing agent of the present invention (especially there is nucleating agent function) by the size adjusting according to process ladle.Such as, there is the ladle of 100-500kg cast iron, preferably set size-grade distribution and be about between 2mm at about 0.4-, and even up to 7mm.For the ladle with 500-1000kg cast iron, preferably set size-grade distribution and be about between 7mm at about 2-, or be about between 30mm at about 10-.For the ladle had more than 1000kg cast iron, preferably set size-grade distribution and be about between 30mm at about 10-.
The embodiment of purposes will be described now.
embodiment 1: the parts that casting A-8mm is thick
casting is with reference to (A1)
According to prior art, by adding star antimony with the ratio of the antimony of liquid cast 30g per ton in induction furnace, process liquid cast.
Subsequently, cast iron is by FeSiMg type inoculant alloy through nodulizing agent process, and this alloy comprises 1/3rd and comprises the FeSiMg alloy and 2/3rds of the rare earth element of 2% without the FeSiMg alloy of rare earth element.
Finally, by adding the FeSiMnZr alloy of by weight 0.1% and the FeSiAl alloy of 0.1% in casting basin, cast iron is through inoculation, and inoculant alloy adds with the nucleating agent form embedded in mould.
use according to inoculant alloy of the present invention (A2)
Ratio with 0.15% of cast iron weight uses the inoculant alloy according to composition 2 mentioned above, and this alloy comprises (by weight): Si=65%Si, Ca=1.76%Ca, Al=1.23%, Sb=0.15%; RE=0.16%, Ba=7.9%.
Eliminate the step of adding star antimony, and only have the inoculant alloy of FeSiMg (this alloy does not comprise rare earth element) to simplify spheroidizing by using.
comparing result
| A1 (reference) | A2 (the application) | |
| Graphite pebbles rate | 95％ | 98％ |
| The matrix (% pearl rock mass) of cast iron | 8％ | 3％ |
| Unit elongation | 15％ | 18％ |
Show in test sample book for the stretch percentage elongation that EN-GJS-400-15 level improves according to the casting A of nucleating agent process of the present invention.
embodiment 2: the parts that casting B-200mm is thick
casting is with reference to (B1)
According to prior art, by adding star antimony with the ratio of the antimony of liquid cast 20g per ton in induction furnace, process liquid cast.
Subsequently, cast iron is by FeSiMg type inoculant alloy through nodulizing agent process, and this alloy comprises the rare earth element of by weight 1% and introduces cast iron with the form of powder cored filament material.
Finally, by adding the FeSiBiRE alloy of by weight 0.15% in casting basin, cast iron is through inoculation.
use the inoculant alloy (B2) according to the application
Ratio with 0.15% of cast iron weight uses the inoculant alloy according to composition 2 mentioned above, and this alloy comprises, as above: Si=65%Si, Ca=1.76%Ca, Al=1.23%, Sb=0.15%; RE=0.16%, Ba=7.9%.
Eliminate the step of adding star antimony, and by only using the inoculant alloy of FeSiMg (this alloy does not comprise rare earth element, also introduces with the form of powder cored filament material) to simplify nodulizing agent process.
comparing result
| B1 (reference) | B2 (the application) | |
| Graphite pebbles rate | 91％ | 97％ |
| The matrix (% pearl rock mass) of cast iron | 4％ | 3％ |
| " short and thick " graphite defect | 15％ | 0％ |
| The restorer of-20 DEG C | 7J | 12J |
Be placed in the result of shock resistance, cast iron B2 has reached satisfactory result.
embodiment 3: the parts (thickness is less than 6mm) that casting C-is thin
casting is with reference to (C1)
According to prior art, by adding star antimony with the ratio of the antimony of liquid cast 25g per ton in induction furnace, process liquid cast.
Subsequently, cast iron is by FeSiMg type inoculant alloy through nodulizing agent process, and this alloy comprises the rare earth element of the magnesium of 6.7% by weight and the calcium of 1.2% and 0.98%.
Finally, by add by weight 0.12% there is the FeSiMnZrBa alloy of size-grade distribution between 0.2-5mm, cast iron is through late inoculation process.
use the inoculant alloy (C2) with nodulizing agent function according to the application
Employ the inoculant alloy with nucleating agent function according to composition 3 mentioned above.
Identical with previous embodiment, eliminate the step of adding star antimony.
Carry out spheroidizing by the FeSiMg type alloy of the composition 3 according to the application, this alloy comprises the magnesium of 6.4% and the calcium of 1.3%, the antimony of 0.6% and the rare earth element of 1.2% by weight.
Use the FeSiAlCa alloy of 0.09% and the FeSiMnZrBa alloy of 0.009% to carry out supplemented according to inoculation method below and bred.
comparing result
| C1 (reference) | C2 (the application) | |
| Graphite pebbles rate | 93％ | 98％ |
| The matrix (% pearl rock mass) of cast iron | 15％ | 4/5％ |
| " short and thick " graphite defect | 4％ | 0％ |
When using the nodulizing agent according to the application, it is to be noted that " short and thick " graphite defect disappears in the parts of all control.
Therefore, likely by using more economic FeSiAlCa type nucleating agent to carry out extra breeding (late inoculation).
embodiment 4: the large parts of casting D-
casting is with reference to (D1)
According to prior art, by adding star antimony with the ratio of the antimony of liquid cast 30g per ton in induction furnace, process liquid cast.
Subsequently, cast iron is by FeSiMg type inoculant alloy through spheroidizing, and this alloy comprises the rare earth element of the magnesium of 9.1% by weight and the calcium of 1.4% and 1.1%.
Finally, added by the form of the cast iron 10kg inset of FeSiMnZr inoculant alloy per ton, cast iron is through inoculation.
use the inoculant alloy (D2) according to the application
With with reference to identical form, use according to the inoculant alloy of composition 2 mentioned above with the form of 10kg inset, and this alloy comprises: Si=65%Si, Ca=1.76%Ca, Al=1.23%, Sb=0.15%; RE=0.16%, Ba=7.9%.
Identical with previous embodiment, eliminate the step of adding star antimony.
By having carried out spheroidizing with reference to identical alloy, namely by using FeSiMg type inoculant alloy, this alloy comprises the rare earth element of the magnesium of 9.1% by weight and the calcium of 1.4% and 1.1%.
comparing result
Cast iron D can prepare EN-GJS-400-18-LT level cast iron, is particularly useful for wind energy field.Use and significantly can increase shock resistance according to the nucleating agent of the application.
embodiment 5: the parts that casting E-is thin add nodulizing agent process
casting is with reference to (E1)
Liquid cast is by FeSiMg type inoculant alloy through nodulizing agent process, and this alloy comprises the rare earth element of the magnesium of 9.1% by weight and the bismuth of 0.8% and 0.7%.
Subsequently, by adding the FeSiMnZr alloy (it has size-grade distribution between 0.2-5mm) of 0.18%, cast iron according to inoculation method subsequently through inoculation.
use the inoculant alloy (E2) with nodulizing agent function according to the application
Use the inoculant alloy according to composition 3 mentioned above.The alloy used is FeSiMg type alloy, and this alloy comprises the rare earth element with the magnesium of 9.1% and the antimony of 0.75% and 0.5%.
Subsequently, by adding the FeSiMnZr alloy (size-grade distribution had is between 0.2-5mm) of 0.17%, according to inoculation method cast iron subsequently through extra inoculation.
comparing result
| E1 (reference) | E2 (the application) | |
| Graphite pebbles rate | 91％ | 95％ |
| " short and thick " graphite defect | 2％ | 0％ |
| The efficiency of magnesium | 54％ | 69％ |
As the above-mentioned, substitute bismuth observe by using antimony, the efficiency of magnesium in cast iron E increases.
embodiment 6: D is on large parts in casting
Use the casting that realizes according to the inoculant alloy of the application with reference to (F1) and test (F2) and the embodiment 4 by breeding large parts and to cast D consistent.
comparing result
| F1 (reference) | F2 (the application) | |
| The efficiency of antimony | 67％ | 98％ |
Can observe, owing to realizing high-level efficiency, the amount adding antimony can be controlled better.Decrease 31.5% by the addition of antimony, casting F2 can be significantly cost-saving.
embodiment 7: D is on large parts in casting
Use the casting that realizes according to the inoculant alloy of the application with reference to (G1) and test (G2) and the embodiment 4 by breeding large parts and to cast D consistent.
comparing result
| G1 (reference) | G2 (the application) | |
| Antimony discharges 8 hours | 0.7mg/m 3 | 0.1mg/m 3 |
Can observe, due to the nucleating agent according to the application, the release of antimony is significantly limited and far below standard cut-off value 0.5mg/m
3.Therefore working conditions is improved.
embodiment 8: the parts that casting H-150mm is thick
casting is with reference to (H1)
According to prior art, by adding star antimony with the ratio of the antimony of liquid cast 15g per ton in induction furnace, process liquid cast.
Subsequently, by nodulizing agent powder cored filament material (13mm diameter, the Mg of 32%, the powder of the RE of 1.2%, 230g/m), cast iron have passed through spheroidizing.
Finally, by adding the FeSiMnZr inoculant alloy of by weight 0.15% in casting bed, cast iron have passed through late inoculation process.
use the inoculant alloy (H2) according to the application
With the ratio of 0.2% of cast iron weight, employ according to the inoculant alloy of composition 1 mentioned above that [this alloy comprises Si=64%Si, Ca=1.64%Ca, Al=1.15%, Sb=0.5%; RE=0.3%].
Eliminate the step of adding star antimony, and by only using the inoculant alloy of FeSiMg (this alloy does not comprise rare earth element, and introduces with the form of powder cored filament material) to simplify nodulizing agent process.
comparing result
| H1 (reference) | H2 (the application) | |
| Graphite pebbles rate | 87％ | 98％ |
| The matrix (% pearl rock mass) of cast iron | 3％ | 3％ |
| " short and thick " graphite defect | 19％ | 0％ |
| The restorer of-20 DEG C | 4J | 14J |
According to shock resistance result, cast iron H2 has reached satisfactory result.
Although be described specific embodiment, and do not mean that the present invention is limited to this and its all technology be equal to the method described be included in the scope of the present invention and combination thereof.
Claims (12)
1., for the treatment of an inoculant alloy for thick ferrosilicon base cast iron member, described inoculant alloy comprises the rare earth element by weight between 0.005-3%, it is characterized in that, described inoculant alloy also comprises the antimony by weight between 0.2-2%.
2. inoculant alloy according to claim 1, is characterized in that, described inoculant alloy also comprises magnesium and composition inoculant alloy.
3. inoculant alloy according to claim 1, is characterized in that, described inoculant alloy does not comprise magnesium.
4. the inoculant alloy according to any one of claim 1-3, is characterized in that, the ratio of rare earth element and antimony is between 0.9-2.2.
5. the inoculant alloy according to any one of claim 1-4, is characterized in that, the weight ratio of antimony higher than 0.3%, preferably higher than 0.5%, more preferably higher than 0.8%.
6. the inoculant alloy according to any one of claim 1-5, is characterized in that, the weight ratio of antimony lower than 1.5%, preferably lower than 1.3%.
7. the inoculant alloy according to any one of claim 1-6, is characterized in that, rare earth element comprises lanthanum, preferably only has lanthanum.
8. the inoculant alloy according to any one of claim 1-7, is characterized in that, the weight ratio of rare earth element higher than 0.2%, preferably higher than 0.3%.
9. the inoculant alloy according to any one of claim 1-7, is characterized in that, the weight ratio of rare earth element lower than 1.2%, preferably lower than 1%.
10. the purposes of the nucleating agent according to aforementioned any one claim, is characterized in that, described nucleating agent is introduced in the form of a powder.
The purposes of 11. nucleating agents according to aforementioned any one claim, is characterized in that, described nucleating agent is introduced with the form of setting solid in the mould.
The purposes of 12. nucleating agents according to aforementioned any one claim, for the manufacture of the cast iron member having thickness and be greater than the part of 6mm, preferably has the part that thickness is greater than 20mm, more preferably has the part that thickness is greater than 50mm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1260817A FR2997962B1 (en) | 2012-11-14 | 2012-11-14 | INOCULATING ALLOY FOR THICK PIECES IN CAST IRON |
| FR12/60817 | 2012-11-14 | ||
| PCT/FR2013/052710 WO2014076404A1 (en) | 2012-11-14 | 2013-11-12 | Inoculant alloy for thick cast-iron parts |
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| CN104812922A true CN104812922A (en) | 2015-07-29 |
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| US (1) | US20150284830A1 (en) |
| EP (1) | EP2920335B1 (en) |
| JP (1) | JP2016503460A (en) |
| KR (1) | KR20150083998A (en) |
| CN (1) | CN104812922A (en) |
| BR (1) | BR112015010975A2 (en) |
| CA (1) | CA2889124C (en) |
| DK (1) | DK2920335T3 (en) |
| ES (1) | ES2777934T3 (en) |
| FR (1) | FR2997962B1 (en) |
| MX (1) | MX2015006053A (en) |
| PL (1) | PL2920335T3 (en) |
| PT (1) | PT2920335T (en) |
| SI (1) | SI2920335T1 (en) |
| UA (1) | UA116218C2 (en) |
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| CN107532225A (en) * | 2015-05-18 | 2018-01-02 | 东芝机械株式会社 | Iron metal liquation processing method |
| CN111809103A (en) * | 2020-07-21 | 2020-10-23 | 常州钜苓铸造有限公司 | Preparation method of high-power wind power ultrahigh-strength high-toughness low-temperature nodular cast iron |
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| CN105039631A (en) * | 2015-08-20 | 2015-11-11 | 合肥市田源精铸有限公司 | Nucleating agent containing rare earth and application of nucleating agent to spheroidal graphite cast iron smelting |
| US10662510B2 (en) | 2016-04-29 | 2020-05-26 | General Electric Company | Ductile iron composition and process of forming a ductile iron component |
| US10787726B2 (en) * | 2016-04-29 | 2020-09-29 | General Electric Company | Ductile iron composition and process of forming a ductile iron component |
| NO20161094A1 (en) | 2016-06-30 | 2018-01-01 | Elkem As | Cast Iron Inoculant and Method for Production of Cast Iron Inoculant |
| NO347571B1 (en) | 2016-06-30 | 2024-01-15 | Elkem Materials | Cast Iron Inoculant and Method for Production of Cast Iron Inoculant |
| NO20172063A1 (en) | 2017-12-29 | 2019-07-01 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| NO346252B1 (en) | 2017-12-29 | 2022-05-09 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| NO20172065A1 (en) | 2017-12-29 | 2019-07-01 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| NO20172064A1 (en) | 2017-12-29 | 2019-07-01 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| NO20172061A1 (en) | 2017-12-29 | 2019-07-01 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| WO2022202914A1 (en) * | 2021-03-24 | 2022-09-29 | 日立金属株式会社 | Spheroidal graphite cast iron, spheroidal graphite cast iron manufacturing method, and spheroidizing treatment agent |
| CN115029495A (en) * | 2022-06-15 | 2022-09-09 | 宜昌佳晟鑫铁合金有限公司 | Pearlite inoculant formula |
| CN115896604A (en) * | 2022-11-15 | 2023-04-04 | 宜昌佳晟鑫铁合金有限公司 | Silicon-based inoculant material proportioning method |
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| CN111809103A (en) * | 2020-07-21 | 2020-10-23 | 常州钜苓铸造有限公司 | Preparation method of high-power wind power ultrahigh-strength high-toughness low-temperature nodular cast iron |
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| KR20150083998A (en) | 2015-07-21 |
| US20150284830A1 (en) | 2015-10-08 |
| CA2889124A1 (en) | 2014-05-22 |
| SI2920335T1 (en) | 2020-03-31 |
| EP2920335A1 (en) | 2015-09-23 |
| WO2014076404A1 (en) | 2014-05-22 |
| EP2920335B1 (en) | 2019-12-18 |
| UA116218C2 (en) | 2018-02-26 |
| ZA201503205B (en) | 2016-10-26 |
| PT2920335T (en) | 2020-03-17 |
| MX2015006053A (en) | 2015-11-23 |
| BR112015010975A2 (en) | 2017-07-11 |
| FR2997962B1 (en) | 2015-04-10 |
| JP2016503460A (en) | 2016-02-04 |
| CA2889124C (en) | 2020-12-29 |
| PL2920335T3 (en) | 2020-05-18 |
| ES2777934T3 (en) | 2020-08-06 |
| DK2920335T3 (en) | 2020-03-16 |
| FR2997962A1 (en) | 2014-05-16 |
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