CN102851575B - Oxidation-resistant alloying grey cast iron and preparation method thereof - Google Patents

Oxidation-resistant alloying grey cast iron and preparation method thereof Download PDF

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CN102851575B
CN102851575B CN201210357807.1A CN201210357807A CN102851575B CN 102851575 B CN102851575 B CN 102851575B CN 201210357807 A CN201210357807 A CN 201210357807A CN 102851575 B CN102851575 B CN 102851575B
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iron
cast iron
oxidation
alloying
grey cast
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CN102851575A (en
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刘希琴
刘子利
钱燕
张全林
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SUZHOU DONGHAI GLASS MOULD CO Ltd
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SUZHOU DONGHAI GLASS MOULD CO Ltd
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Abstract

The invention discloses an oxidation-resistant alloying grey cast iron and a preparation method of the oxidation-resistant alloying grey cast iron. The cast iron comprises the following components by mass percentage: 3.0-3.2% of C, 1.8-2.0% of Si, 0.50-0.70% of Mn, 0.10-0.50% of Cr, 0.20-0.30% of Ni, 0.03-0.50% of Mo, 0.5-3.0% of Al, 0.05-0.08% of Sr, 0.005-0.15% of Zn, and the balance of Fe and inevitable impurities. The preparation method comprises the steps of melting raw materials, culturing and processing, and pouring, wherein the tapping is carried out at 1450 to 1550 DEG C after melting; the molten iron is processed by being flushed in a ladle and cultured and processed along with the flow, and then slagged and casted. According to the oxidation-resistant alloying grey cast iron provided by the invention, the organization of the grey alloying cast iron material is structured by distributing 6-8 grades of D type graphite with little graphite of A type on a ferrite substrate, so that higher toughness, high heat conductivity and high-temperature oxidization resistance can be achieved, and good casting technical performance can be ensured as well; and the oxidation-resistant alloying grey cast iron can be applied to manufacturing a glass die and a light alloy metal type casting die which can bear the heat impacting of high-temperature formed liquid and cold-heat alternating stress for a long time.

Description

Oxidation-resistance alloying grey cast iron and preparation method thereof
Technical field
The present invention relates to a kind of oxidation-resistance alloying grey cast iron, this grey cast iron is applicable to prepare glasswork manufacture, permanent mold casting etc. and bears for a long time that hot forming heat of liquid is impacted and the mould of alternating hot and cold stress, belongs to heating resisting metal material technology field.The invention still further relates to the preparation method of above-mentioned oxidation-resistance alloying grey cast iron.
Background technology
Metal is worked under hot conditions, conventionally can produce the phenomenons such as oxidation and growth.Oxidation refers to the at high temperature erosion of oxidated property atmosphere, produces oxidation peeling in metallic surface, and the useful area that reduces metal because of face reduces the supporting capacity of foundry goods.What growth referred to that metal at high temperature occurs produces irreversible volume and grows up because chemical metallurgy changes, and causes accessory size to increase and makes mechanical property reduction.
For bearing for a long time, hot forming heat of liquid is impacted and the glass mold of alternating hot and cold stress, light alloy metal mold casting die, mould contacts hot forming molten materials continually, not only under hot soak condition, work, and in die sinking repeatedly, in the process of matched moulds, produce friction, therefore, moulding stock not only requires dense structure even, should have good heat-resisting, wear-resisting, corrosion-resistant, thermal fatigue resistance, anti-oxidant, antibiosis is long, thermal conductivity is good, linear expansivity is little, the performances such as sticking temperature height, should there is in addition good machining property and surface smoothness.
Cast iron is because its cheap price is with well casting and mechanical processing technique performance have obtained application the most widely, intensity, heat-resistant anti-fatigue performance, anti-oxidant growth performance, the heat conductivility of the microtexture (being composition, the size of crystal grain, the size of graphite, the distribution of shapes of matrix) of cast iron on cast iron has direct impact, thereby determined the use properties of moulding stock.
The oxidation of cast iron refers to that graphite destroys as the burning of carbonaceous material under high temperature oxidation stability atmosphere, and graphite is thicker, and graphite form is more continuous, and the more, the oxidation of cast iron is just more serious for graphite.When graphite is sheet, it is inner and be easily oxidized that oxidizing atmosphere is invaded foundry goods along graphite flake, and during globular graphite, because graphite pebbles is discontinuous mutually, oxidizing atmosphere is just difficult for invading along graphite, so the oxidation-resistance of spheroidal graphite cast iron is always good than the grey cast iron of flake graphite.
But nodular cast iron is isolate spherical as the graphite of main heat transfer path, form very large thermal resistance, cause the poor thermal conductivity of spheroidal graphite cast iron.The thermal conductivity of Cast Iron Die is less, and temperature fluctuation range during mold work is just larger, thereby not only makes the Quality Down of product, and higher alternating hot and cold thermal stresses work-ing life of having reduced mould.
Although have more high-intensity performance, the cast iron of pearlite matrix is separated out the volume of cast iron is swollen in the greying producing lower than the pearlite decomposition under transformation temperature, and the long Performance Ratio ferrite matrix of the antibiosis cast iron of pearlite matrix cast iron is poor.On the other hand, the graphite-phase quantity of ferrite matrix cast iron is more than pearlite matrix cast iron, its good heat conductivity.Therefore, the grey cast iron of ferrite matrix becomes the best cast iron die material of similar application such as preparing glasswork, permanent mold casting.
But, in the poor and use procedure of the polishing performance of regular gray iron, because anti-oxidant and the low die surface that easily makes of growth performance produce the defects such as be full of cracks, cause mould to be scrapped.By alloying and structure refinement, to obtain thermal conductivity and the more excellent alloying grey cast iron of oxidation-resistance, become the important directions of these series mould material research and development.
Cr has improved the phase point temperature changing also forms fine and close continuously oxide film, become the important alloy element of heat resisting iron, for example, document CN85108041A(glass mold material and production technique thereof) announce low-alloy grey-cast iron moulding stock, CN101914720A(high-alloy black iron glass mold and manufacture method thereof), CN1405353A(novel casting and hot work tool steel), CN102676908A (rare earth nucleating agent promotes the alloy glass mold of D type graphite), CN102560230A (utilizing steel scrap to substitute the alloy glass mold of pig iron smelting D-type graphite) and CN101942619A (alloy cast iron glass mold material and preparation method thereof) etc.Above-mentioned novel die material all, using one or more elements in Cr, Ni, Mo, Cu as main alloy element, hinders graphited element while being eutectoid transformation due to these elements, the quantity of matrix Medium pearlite will increase, and the quantity of graphite reduces.
Although Mo, Ni, Cr alloying element have the effect of stabilizing pearlite, but concerning high melting point glass material, dystectic molten metal permanent mold casting and large mould, pearlite matrix is still unstable, its greying precipitation process will cause the growth of cast iron, therefore, in alloy substrate, oxidation-resistance and heat conductivility are lower, and the use properties of mould declines.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of take ferrite as matrix alloy grey cast iron by alloying means, and its anti-oxidant growth performance and heat conductivility are significantly better than the heat-resistance grey cast iron in prior art.The present invention also provides a kind of preparation method of oxidation-resistance alloying grey cast iron, and the method preparation requires comprehensive embodiment of the technique effect of not harsh and energy low cost guarantee alloy.The method both favourable refinement alloy structure forms to obtain tiny uniform D type graphite, is conducive to that alloying element solid solution is avoided in matrix forming free alloy carbide and the processability and the use properties that affect alloy simultaneously.
In order to solve above-mentioned technical problem, technical scheme of the present invention is: a kind of oxidation-resistance alloying grey cast iron, the component that it comprises following mass percent: C 3.0~3.2%, Si 1.8~2.0%, Mn 0.50~0.70%, Cr 0.10~0.50%, Ni 0.20~0.30%, Mo 0.30~0.50%, Al0.5~3.0%, Sr 0.05~0.08%, Zn 0.005~0.015%, all the other are Fe and inevitable impurity, wherein P≤0.1%, S≤0.1%.
The tensile strength of described grey cast iron is 220~270MPa, and Brinell hardness is 160~240HBW, and the oxidation-resistance at 750 ℃ is 2.2~4.5g/mm 2h.
The preparation method of oxidation-resistance alloying grey cast iron of the present invention comprises the following steps:
(1) batching: steel scrap, foundry iron, ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron, fine aluminium, electrolytic nickel, Al-Sr master alloy furnace charge are carried out to chemical composition analysis, then by following mass percent, take above-mentioned furnace charge and be configured in melting in medium-frequency induction furnace: C 3.0~3.2%, Si 1.8~2.0%, Mn 0.50~0.70%, Cr 0.10~0.50%, Ni 0.20~0.30%, Mo 0.30~0.50%, Al 0.5~3.0%, Sr 0.05~0.08%, all the other are Fe and inevitable impurity (P≤0.1%, S≤0.1%); Described foundry iron, ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron are the trade mark furnace charge of GB regulation, Al-Sr master alloy adopts the Al-10%Sr master alloy that Sr quality percentage composition is 10%, during batching, according to Sr content, determine required Al-Sr master alloy, then the quality of the corresponding fine aluminium that calculates required supplementary interpolation.
(2) melting: will weigh steel scrap, foundry iron by proportioning and put into medium frequency induction melting furnace heating completely after fusing, then ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron furnace charge and electrolytic nickel added to melt and adjust molten iron temperature tapping temperature be 1450 ℃ ~ 1550 ℃.
(3) inoculation and cast: will account for 4 ~ 6mm zinc particle of furnace charge gross weight 0.1 ~ 0.3%, be placed in the bottom of casting ladle or the pit of pit type spheroidizing bag by 10 ~ 20mm aluminium block of industrial aluminium ingot fragmentation and 10 ~ 20mm Al-10%Sr master alloy of 0.5 ~ 0.8%, and then cover with foundary weight sheet; The molten iron having melted is joined in casting ladle, add 4 ~ 8mm 75SiFe nucleating agent with stream, the add-on of nucleating agent accounts for 0.2 ~ 0.4% of molten iron gross weight simultaneously; Finally, the molten iron in casting ladle is skimmed, poured into a mould.
The beneficial effect of technical scheme provided by the invention is:
(1) from the resistance toheat and tissue design of alloy, Al is as improving alloy resistance toheat and strongly promoting that graphited alloying element of all stages is incorporated in alloy, when adjustment alloying constituent is with Cr, Mo, Ni beneficial effect in retaining alloy, while having overcome eutectoid transformation, hinder the disadvantageous effect that greying promotes that matrix Medium pearlite forms, the matrix that makes alloy is ferrite matrix, therefore, not only improved the work-ing life of mould, and removed existing alloy grey cast iron must adopt annealing treating process, reduced cost.
Super cooling tendency when low alloy carbon equivalent is conducive to increase alloy graining and promote the formation of D type graphite, in alloy of the present invention, C content is 3.0~3.2%, Si content is 1.8~2.0%.Because impelling cast iron, Mn obtains pearlitic structure, therefore the Mn content in alloy of the present invention only has Mn 0.50~0.70%.Because the every increase of Al 1% makes the phase point temperature (A1 point) changing improves 50 ℃, and Al slackened the binding ability between iron-carbon atom, and below 4%, its graphitizability increases with the rising of content, thereby in alloy, the quantity of ferrite and graphite increases; Also consider the light specific gravity of aluminium, too high Al content easily produces oxidization burning loss, segregation and contraction in fusion process simultaneously, and therefore the add-on of Aluminum in Alloy of the present invention is 0.5~3.0%.Cr is as carbide forming element, its content has hindered eutectic graphite process 0.5 ~ 1.0%, when Cr exists and Al comprehensive action not only significantly promote the resistance toheat of alloy, and segregation and the contraction problem of Al have been eliminated, consider above-mentioned factor, in alloy of the present invention, the add-on of Cr is 0.10~0.50%.Although Mo, Ni can improve plasticity, oxidation-resistance and the volume stability of alloy, and there is the ability that makes graphite refinement, as perlite stable element, its add-on is difficult for too much, the price of Ni and Mo is comparatively valuable simultaneously, therefore Ni is that 0.20~0.30%, Mo is 0.30~0.50 in alloy.
(2) technical from inoculation, Al is introduced in inoculation process as nucleating agent, has realized comprehensive embodiment of preparing the technique effect that requires not harsh and energy low cost guarantee alloy.
In moulding cast iron die, the distribution of the graphite structure generally fine platy tissue from mould working face gradually becomes the thick lamellar structure at the back side.Such tissue distribution affects its heat conductivility, thereby has increased the danger of hot tearing.Inoculation has been eliminated cast iron interalloy carbide, makes the refinement densification of cast iron crystal grain, and graphite attenuates and be littlely unfavorable for cast iron internal oxidation, thereby is conducive to improve the work-ing life of mould.D type graphite is the tissue that cast iron is separated out under supercooled state, Microstructure characteristics is that tiny dendrite point graphite is distributed on matrix, thereby little to the effect of isolating of matrix, dense structure, thereby D type Graphite Iron Cast has than the better mechanical property of A type graphite cast iron, resistance toheat, machinability and wear resisting property.Carbon equivalent in the molten iron of alloy melting of the present invention is low, contains the alloying elements such as Cr, Ni, Mo simultaneously, thereby has very strong Quench ability, through inoculation, easily obtains D type graphite.
From the understanding of inoculation mechanism and the industrial practice of inoculation, in nucleating agent, contain a certain amount of Al and calcium and can improve the effect of inoculation.It is main nucleating agent the most conventional current-following inoculation of employing that inoculation technology of the present invention adopts the most common 75SiFe, when in casting ladle, molten iron pours, the Al of fusing and the cooperation of Al-Si master alloy have strengthened the effect breeding, avoid inoculation fade adding of Sr simultaneously, reached the effect of commercial long-acting nucleating agent.On the other hand, zinc Patterns for Close-Packed Hexagonal Crystal structure, its fusing point is 419.5 ℃, boiling point is 906 ℃.During inoculation, zinc adds formation steam can promote being uniformly distributed of nucleating agent, also can, by being difficult to the floating of the oxide inclusion reducing, reduce the oxygen level in cast iron, has further strengthened the performance of alloy.
Embodiment
Embodiment 1
By quality per distribution ratio, C 3.2%, Si 2.0%, Mn 0.50%, Cr 0.10%, Ni0.20%, Mo 0.30%, Al0.5%, all the other are Fe and inevitable impurity, join and get alloy material and in 250Kg medium-frequency induction furnace, add and put into medium frequency induction melting furnace heating completely after fusing by weighed steel scrap, the Z18 cast iron pig iron by proportioning, then FeSi45 ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron furnace charge and electrolytic nickel are added to melt and adjust molten iron temperature tapping temperature be 1450 ℃;
Inoculation and cast: by the zinc particle (5mm size) that accounts for furnace charge gross weight 0.1% (in inoculation process, under the effect of high temperature liquid iron, zinc will gasify strongly, its residual rate in aluminium alloy is only 5% left and right of add-on, following embodiment is in like manner), by the aluminium block (10mm size) of industrial aluminium ingot fragmentation and 0.5% Al-10%Sr master alloy (10mm size), be placed in the bottom of casting ladle or the pit of pit type spheroidizing bag, then with foundary weight sheet, cover; The molten iron having melted is joined in casting ladle, add 4mm size 75SiFe nucleating agent simultaneously with stream, the add-on of nucleating agent accounts for 0.2% of molten iron gross weight.Finally, the molten iron in casting ladle is skimmed, poured into a mould.
After tested this alloy be organized as the D type graphite that distributing on ferrite matrix, graphite length rank is 6 grades; Performance is: tensile strength is 220MPa, and Brinell hardness is 160HBW, the oxidation-resistances of 750 ℃, is 2.2g/mm 2h.
Embodiment 2
By quality per distribution ratio, C 3.0%, Si 1.8%, Mn 0.70%, Cr 0.50%, Ni0.30%, Mo 0.50%, Al3.0%, all the other are Fe and inevitable impurity, join and get alloy material and in 500Kg medium-frequency induction furnace, add and put into medium frequency induction melting furnace heating completely after fusing by weighed steel scrap, the Z18 cast iron pig iron by proportioning, then FeSi45 ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron furnace charge and electrolytic nickel are added to melt and adjust molten iron temperature tapping temperature be 1550 ℃;
Inoculation and cast: will account for the zinc particle (4mm size) of furnace charge gross weight 0.3%, by the aluminium block (20mm size) of industrial aluminium ingot fragmentation and 0.8% Al-10%Sr master alloy (20mm size), be placed in the bottom of casting ladle or the pit of pit type spheroidizing bag, then with foundary weight sheet, cover; The molten iron having melted is joined in casting ladle, add 8mm size 75SiFe nucleating agent simultaneously with stream, the add-on of nucleating agent accounts for 0.4% of molten iron gross weight.Finally, the molten iron in casting ladle is skimmed, poured into a mould.
After tested this alloy be organized as the D type graphite that distributing on ferrite matrix, graphite length rank is 8 grades; Performance is: performance is: tensile strength is 270MPa, and Brinell hardness is 240HBW, the oxidation-resistances of 750 ℃, is 4.5g/mm 2h.
Embodiment 3
By quality per distribution ratio, all the other are Fe and inevitable impurity for C 3.1%, Si 1.9%, Mn 0.60%, Cr 0.30%, Ni0.25%, Mo 0.40%, Al1.5%, join and get alloy material and in 250Kg medium-frequency induction furnace, add and put into medium frequency induction melting furnace heating completely after fusing by weighed steel scrap, the Z18 cast iron pig iron by proportioning, then FeSi45 ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron furnace charge and electrolytic nickel are added to melt and adjust molten iron temperature tapping temperature be 1500 ℃;
Inoculation and cast: will account for the zinc particle (6mm size) of furnace charge gross weight 0.2%, by the aluminium block (15mm size) of industrial aluminium ingot fragmentation and 0.7% Al-10%Sr master alloy (15mm size), be placed in the bottom of casting ladle or the pit of pit type spheroidizing bag, then with foundary weight sheet, cover; The molten iron having melted is joined in casting ladle, add 6mm size 75SiFe nucleating agent simultaneously with stream, the add-on of nucleating agent accounts for 0.3% of molten iron gross weight.Finally, the molten iron in casting ladle is skimmed, poured into a mould.
After tested this alloy be organized as the D type graphite that distributing on ferrite matrix, graphite length rank is 7 grades; Performance is: tensile strength is 250MPa, and Brinell hardness is 205HBW, the oxidation-resistances of 750 ℃, is 3.4g/mm 2h.
Above-described embodiment does not limit the present invention in any way, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops in protection scope of the present invention.

Claims (4)

1. an oxidation-resistance alloying grey cast iron, it is characterized in that the component that comprises following mass percent: C 3.0~3.2%, Si 1.8~2.0%, Mn 0.50~0.70%, Cr 0.10~0.50%, Ni 0.20~0.30%, Mo 0.30~0.50%, Al0.5~3.0%, Sr 0.05~0.08%, Zn 0.005~0.015%, all the other are Fe and inevitable impurity.
2. oxidation-resistance alloying grey cast iron according to claim 1, the tensile strength that it is characterized in that described grey cast iron is 220~270MPa, and Brinell hardness is 160~240HBW, and the oxidation-resistance at 750 ℃ is 2.2~4.5g/mm 2h.
3. a preparation method for oxidation-resistance alloying grey cast iron, is characterized in that:
(1) batching: steel scrap, foundry iron, ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron, fine aluminium, electrolytic nickel, Al-Sr master alloy furnace charge are carried out to chemical composition analysis, then by following mass percent, take above-mentioned furnace charge and be configured in melting in medium-frequency induction furnace: C 3.0~3.2%, Si 1.8~2.0%, Mn 0.50~0.70%, Cr 0.10~0.50%, Ni 0.20~0.30%, Mo 0.30~0.50%, Al 0.5~3.0%, Sr 0.05~0.08%, all the other are Fe and inevitable impurity;
(2) melting: will weigh steel scrap, foundry iron by proportioning and put into medium frequency induction melting furnace heating completely after fusing, then ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron furnace charge and electrolytic nickel added to melt and adjust molten iron temperature tapping temperature be 1450 ℃ ~ 1550 ℃;
(3) inoculation and cast: will account for 4 ~ 6mm zinc particle of furnace charge gross weight 0.1 ~ 0.3%, be placed in the bottom of casting ladle or the pit of pit type spheroidizing bag by 10 ~ 20mm aluminium block of industrial aluminium ingot fragmentation and 10 ~ 20mm Al-10%Sr master alloy of 0.5 ~ 0.8%, and then cover with foundary weight sheet; The molten iron having melted is joined in casting ladle, add 4 ~ 8mm 75SiFe nucleating agent with stream, the add-on of nucleating agent accounts for 0.2 ~ 0.4% of molten iron gross weight simultaneously; Finally, the molten iron in casting ladle is skimmed, poured into a mould.
4. the preparation method of oxidation-resistance alloying grey cast iron according to claim 3, it is characterized in that: described foundry iron, ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron are the trade mark furnace charge of GB regulation, Al-Sr master alloy adopts the Al-10%Sr master alloy that Sr quality percentage composition is 10%, during batching, according to Sr content, determine required Al-Sr master alloy, then the quality of the corresponding fine aluminium that calculates required supplementary interpolation.
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