CN110042302A - A kind of anti-corrosion Ultra-low carbon high silicon iron-base alloy and preparation method thereof - Google Patents

A kind of anti-corrosion Ultra-low carbon high silicon iron-base alloy and preparation method thereof Download PDF

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Publication number
CN110042302A
CN110042302A CN201910267379.5A CN201910267379A CN110042302A CN 110042302 A CN110042302 A CN 110042302A CN 201910267379 A CN201910267379 A CN 201910267379A CN 110042302 A CN110042302 A CN 110042302A
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alloy
low carbon
iron
high silicon
corrosion
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Inventor
赵爱民
张月
尹鸿祥
刘伟
孙绍恒
裴伟
郭军
蒋有辉
刘素鹏
李迁
刘逸飞
赵子肖
张宜顺
娄殿川
刘涵赜
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D5/00—Heat treatments of cast-iron
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

A kind of anti-corrosion Ultra-low carbon high silicon iron-base alloy and preparation method thereof, belongs to corrosion resistant alloy field, it is characterised in that its alloy composition (important percentage) are as follows: C≤0.005%；Si 14.4~20.0%；P≤0.008%；S≤0.008%；RE 0.01~0.05%, remaining is Fe and inevitable impurity.Ultra-low carbon high silicon iron-base alloy of the invention the preparation method is as follows: by pure iron, steel scrap, the raw materials such as ferrosilicon are added in electric induction furnace or electric arc furnaces and carry out melting twice, it is sufficiently mixed various materials uniformly, alloy melting temp is 1530~1550 DEG C, tapping temperature is 1450~1480 DEG C, rare earth ferrosilicon alloy is added before coming out of the stove in ladle, using resin bonded sand mould cast form, pouring temperature is 1380~1420 DEG C, after solidification 0.5~1 hour, red move back is carried out immediately, in the state of not unpacking, it is fitted into the heat-treatment furnace for being previously heated to 700~850 DEG C, after heat preservation 2-3 hours, with 5-8 DEG C/h of cooling velocity furnace be as cold as 50 DEG C come out of the stove it is air-cooled.Ultra-low carbon high silicon iron-base alloy prepared in accordance with the present invention has good corrosion resistance, can be used for manufacturing the component contacted with strong corrosive medium.

Description

A kind of anti-corrosion Ultra-low carbon high silicon iron-base alloy and preparation method thereof
Technical field
The present invention relates to a kind of anti-corrosion Ultra-low carbon high silicon iron-base alloy and preparation method thereof, belong to corrosion resistant alloy field.
Background technique
With the development of industry, people are higher and higher for the material requirements being exposed in the equipment in strong corrosive environment. General steel material electrode potential is lower, cannot form dense oxidation film, a large amount of Cr element is added in stainless steel, can be formed Fine and close Cr2O3Passivating film significantly improves the corrosion resistance of alloy, but the Cr in strong oxidizing property acid solution2O3Stability of Passive Film Difference significantly reduces its corrosion resistance, so that the etching problem under strong oxidizing property acid medium receives the concern of people, therefore generates High-silicon cast iron this material.Containing the silicon of high-content in high-silicon cast iron, its surface can form one layer in suitable medium Fine and close SiO2Passivating film, this acidic oxidation film is still very stable in the strong oxidizing properties acid solution such as high-temperature sulfuric acid, nitric acid, because This high-silicon cast iron has excellent corrosion resistance in strong oxidizing property acid medium.High-silicon cast iron is usually used in production and bears dead load The component contacted with various strong corrosive mediums, can be used for the required anti-corrosion casting of the industry such as chemical industry, petroleum, metallurgy, national defence, such as The parts such as the flow passage part of acid-proof pump, various valves in chemical industry, it may also be used for production cold-rolling stainless steel cathodic pickling line sun Pole plate etc..And high-silicon cast iron also has the characteristics of at low cost, simple production process.But there is intensity again for this material , hardness high, brittleness big, thermal coefficient small and the coefficient of expansion big the disadvantages of low with impact flexibility, so that in Foundry Production and application When be easy to generate shrinkage porosite, shrinkage cavity and the defects of crackle, be not amenable to violent temperature change and bear high pressure, be machined ratio More difficult, this limits its application to a certain extent.Contain graphite in existing high-silicon cast iron tissue, due to graphite intensity, Hardness is lower, and plasticity, toughness are very poor, therefore the presence of graphite is equivalent in matrix and is dispersed with many crackles and " cavity ", plays and cuts The effect for splitting matrix greatly reduces its tensile strength, graphite is more, size is coarseer, distribution it is more uneven, then intensity, Plasticity and toughness are lower.And graphite electrode current potential, compared with matrix height, the activity in corrosion process as corrosion galvanic cell is negative Pole, and matrix is accelerated corrosion as anode, therefore the presence of graphite also has detrimental effect to corrosion resistance.Therefore it is based on this Thinking develops in a kind of tissue without the anti-corrosion high silicon iron-base alloy of Ultra-low carbon existing for graphite.
Summary of the invention
The present invention be in order to poor for common casting corrosion resistance, and high-silicon cast iron that there is intensity and impact flexibility is low, The problems such as hardness is high, brittleness is big obtains Ultra-low carbon high silicon iron base existing for a kind of no graphite by effective Design of Chemical Composition Alloy further improves corrosion resisting property.
In order to achieve the above object, Ultra-low carbon high silicon iron-base alloy provided by the invention, chemical component percentage are as follows: C ≤ 0.005%；Si 14.4~20.0%；P≤0.008%；S≤0.008%；RE 0.01~0.05%, remaining is for Fe and not Evitable impurity.
The reason of limiting range to alloying element content of the present invention below is done as described in detail below.
(1) silicon (Si): 14.4~20% (weight)
The present invention selects Si as the main element against corrosion of alloy, silicon be can be formed the fine and close most common element of passivating film it One, there are also Cr and Al for the most common element that can generate dense oxidation film.Cr is generallyd use in stainless steel as passivating film Formation element mainly uses formation element of the Al as passivating film in heat-resisting alloy.In comparison, the oxidation film that silicon is formed There is good stability in strong acid solution, there is excellent corrosion resisting property in strong acid media, and the passivating film containing chromium exists Corrosion resistance is poor in the strong acid solutions such as sulfuric acid or nitric acid.And seldom applied in strong acid media containing alumite, Al mainly applies resistance to In thermalloy.Compared with silicon, the cost is relatively high and the alloy melting of high aluminium content is more difficult for aluminium, thus selected silicon as The passivating film formation element of the ferrous alloy.When silicon content is less, surface not will form one layer of fine and close silica oxygen Change film, corrosion resistance is controlled by iron oxide film.When silicone content reach one timing, will form passivation under ambient condition appropriate Film, and with the increase of silicone content, oxidation film compactness increases, and corrosion resisting property improves.But when silicon content is excessively high, and it is steady to generate Jie Fixed brittlement phase, and as silicone content increases, brittleness phase amount will be further increased, and the toughness of alloy, which will further decrease, makes material Expect more crisp.Therefore in order to obtain good corrosion resistance, and do not make its mechanical performance too poor, the anti-corrosion ferrous alloy of high silicon of design In, silicone content is selected in 14.4%~20%.
(2) carbon (C) :≤0.005% (weight)
Silicone content in alloy should be improved in order to improve its corrosion resistance in the high anti-corrosion ferrous alloy of silicon, silicone content is higher, contains Carbon amounts should be lower.This is because Si is graphite element, solvability ratio C of the Si in solid solution is strong, and Si accelerates again The diffusion of C, therefore C is just expelled from and comes and form graphite.Graphite has cut off the continuity of metallic matrix, due to graphite itself Almost without tensile strength, also without elongation, therefore whole tensile strength is greatly reduced.When the C amount of alloy improves, graphite Increase, increase, just will form more " cavities " and constitute more micro cells, and is unfavorable for its mechanical property and corrosion resistance. So, by reducing carbon content, the C content of the anti-corrosion ferrous alloy of the high silicon of Ultra-low carbon is selected in order to avoid Graphite Precipitation 0.005% or less.
(3) phosphorus: < 0.008% (weight)
P is harmful element in high silicon iron-base alloy, and P will increase the brittleness of alloy and the heat resistance of high silicon corrosion resistant alloy, It should try to control in lower range, the anti-corrosion ferrous alloy of high silicon of the design, P content controls below 0.008%.
(4) sulphur: < 0.008% (weight)
S is harmful element in high silicon iron-base alloy, and S can reduce the corrosion resistance and mechanical performance of high silicon corrosion resistant alloy.Institute It should try to control in lower range with S content, S content is strict controlled in 0.008% or less.
(5) rare earth: 0.01~0.05% (weight)
Rare earth is a kind of active element, and appropriate be added in alloy will generate advantageous effect.Remain in micro- in cast iron Amount rare earth can significantly influence the corrosion resistance of cast iron.It is generally acknowledged that this is because rare earth changes oxidation film in Cast Iron Surface Caused by structure.Rare earth element can also reduce the surface tension of phase interface, to reduce critical nuclei function, improve nucleus and form speed Degree can provide heterogeneous nucleus in crystallization, make crystal grain refinement, thinning solidification structure.The addition of alterant element has desulfating and deoxidation The effect of degasification, can be with purifying molten metal, while can also reduce the casting flaws such as Casting Blowholes, shrinkage cavity, loose, improves casting Part consistency.Rare earth content is added in high silicon iron-base alloy to be determined according to the air content of molten iron, residual in high silicon iron-base alloy Stay content of rare earth control 0.01%~0.05%.
A kind of preparation method of anti-corrosion Ultra-low carbon high silicon iron-base alloy as described above, it is characterised in that preparation process includes Melting, Metamorphism treatment, casting, heat treatment 4 steps, wherein melting using melting twice method, first time melting by pure iron, Steel scrap, ferrosilicon raw material configure alloy, these raw material are added in electric induction furnace or electric arc furnaces after dissolving and are uniformly mixed, casting At ingot, slag former sodium metasilicate, melting temperature is added in fusion process using first time smelting and pouring good ingot in second of melting Degree is 1530~1550 DEG C, and gas and field trash in sufficiently long time removal aluminium alloy are stood after dissolving.
Further, the Metamorphism treatment is carried out in ladle, and after molten alloy, rare earth is added at ladle packet bottom Antaciron, additional amount be handle weight of molten iron 0.5~1.0%, by melted molten iron pour into ladle with rare earth silicon Ferroalloy reaction, tapping temperature are as follows: 1450~1480 DEG C.
Further, the casting is to be cast as using the enclosed running gate system that flows slowly using Resin sand assembled core mold Shape, by the molten iron casting after Metamorphism treatment in the type chamber of resin bonded sand mould, pouring temperature is 1380~1420 DEG C.Using resin Sand cored-up mould is the collapsibility and deformability in order to reinforce casting mold, reduces casting stress, prevents casting process from cracking.
Further, the heat treatment is using red processing of bringing down a fever after casting, after casting solidification shapes 0.5h-1h, not Hot charging enters to be previously heated in 700~850 DEG C of heat-treatment furnaces in the state of unpacking, after heat preservation 2-3 hours, with 5-8 DEG C/h Cooling velocity furnace is as cold as 50 DEG C and comes out of the stove.
Beneficial effects of the present invention: compared with traditional ferrous alloy, with high-content in ferrous alloy of the invention Silicon will form SiO under ambient condition appropriate2Passivating film, improves the corrosion resistance of ferrous alloy, and of the invention iron-based Ultralow carbon content in alloy, avoids the precipitation of graphite in tissue, to further improve the mechanical property of alloy and resistance to Corrosion.
Detailed description of the invention
The process flow chart of Fig. 1 is anti-corrosion Ultra-low carbon high silicon iron-base alloy,
The energization corrosion rate of embodiment and comparative example under Fig. 2 identical experiment parameter.
Specific embodiment
Following specific embodiments are implemented according to alloy composition range set by the present invention and preparation method, in detail It describes in detail and implementation process of the invention is illustrated, be merely to illustrate and explain the present invention, be not intended to restrict the invention.
Embodiment 1:
A kind of chemical component (weight percent) of anti-corrosion Ultra-low carbon high silicon iron-base alloy are as follows: carbon 0.004%, silicon 16.2%, phosphorus < 0.008%, sulphur < 0.008%, RE 0.05%, surplus is iron and inevitable impurity.Its preparation process and Heat treatment process is as follows:
(1) melting: using the method for melting twice, the raw material such as pure iron, steel scrap, ferrosilicon are configured and are closed by first time melting These raw material are added in electric induction furnace or electric arc furnaces after dissolving and are uniformly mixed by gold, pour into ingot, and second of melting uses Slag former sodium metasilicate is added in fusion process for first time smelting and pouring good ingot, and smelting temperature is 1530 DEG C, stands after dissolving Gas and field trash in sufficiently long time removal aluminium alloy.
(2) Metamorphism treatment: carrying out Metamorphism treatment using ladle, and after molten alloy, rare earth silicon is added at ladle packet bottom Ferroalloy, additional amount be handle weight of molten iron 0.5~1.0%, by melted molten iron pour into ladle with rare earth ferrosilicon Alloy reaction, tapping temperature are as follows: 1460 DEG C.
(3) it is poured: by the type chamber of the molten iron casting after Metamorphism treatment to resin bonded sand mould, carrying out cast form.Casting temperature Degree is 1380 DEG C of temperature.
(4) heat treatment process: using red processing of bringing down a fever after casting, after casting solidification shapes 0.5h, in not unpacking state Lower hot charging enters in the heat-treatment furnace for being previously heated to 800 DEG C, after heat preservation 3 hours, is as cold as 50 with 7 DEG C/h of cooling velocity furnace It DEG C comes out of the stove.
Embodiment 2:
A kind of chemical component (weight percent) of anti-corrosion Ultra-low carbon high silicon iron-base alloy are as follows: carbon 0.005%, silicon 15.05%, phosphorus < 0.008%, sulphur < 0.008%, RE 0.03%, surplus is iron and inevitable impurity.Its preparation process and Heat treatment process is as follows:
(1) melting: using the method for melting twice, the raw material such as pure iron, steel scrap, ferrosilicon are configured and are closed by first time melting These raw material are added in electric induction furnace or electric arc furnaces after dissolving and are uniformly mixed by gold, pour into ingot, and second of melting uses Slag former sodium metasilicate is added in fusion process for first time smelting and pouring good ingot, and smelting temperature is 1550 DEG C, stands after dissolving Gas and field trash in sufficiently long time removal aluminium alloy.
(2) Metamorphism treatment: carrying out Metamorphism treatment using ladle, and after molten alloy, rare earth silicon is added at ladle packet bottom Ferroalloy, additional amount be handle weight of molten iron 0.5~1.0%, by melted molten iron pour into ladle with rare earth ferrosilicon Alloy reaction, tapping temperature are as follows: 1480 DEG C.
(3) it is poured: the molten iron after Metamorphism treatment being poured onto note into the type chamber of resin bonded sand mould, carries out cast form.Casting Temperature is 1400 DEG C of temperature.
(4) heat treatment process: using red processing of bringing down a fever after casting, after casting solidification shapes 1h, in the state of not unpacking Hot charging enters in the heat-treatment furnace for being previously heated to 850 DEG C, after heat preservation 3 hours, is as cold as 50 DEG C with 5 DEG C/h of cooling velocity furnace It comes out of the stove.
Comparative example:
A kind of chemical component of high-silicon cast iron (weight percent) are as follows: carbon 0.49%, silicon 16.02%, phosphorus < 0.01%, sulphur < 0.01%, copper 7.72%, surplus is iron and inevitable impurity.
Using the method for the corrosion that is powered, identical electrolyte is selected, sets identical electrolytic parameter, weight loss is measured, obtains Corrosion rate result to material sample of the present invention under identical experiment parameter and comparison high-silicon cast iron sample is as shown in Figure 2.From It can be seen that the corrosion rate of material of the present invention is below the corrosion rate of high-silicon cast iron in figure, with the increase of conduction time, Corrosion rate is reduced and is tended to be steady, and the corrosion rate of embodiment is about the half of comparative example corrosion rate, i.e., material of the present invention Corrosion resisting property be substantially better than the corrosion resisting property of high-silicon cast iron.

Claims (5)

1. a kind of anti-corrosion Ultra-low carbon high silicon iron-base alloy, it is characterised in that its chemical component weight percentage are as follows: C≤0.005%； Si14.4~20%；P≤0.008%；S≤0.008%；RE0.01~0.05%, remaining is Fe and inevitable impurity.
2. the preparation method of anti-corrosion Ultra-low carbon high silicon iron-base alloy according to claim 1, it is characterised in that preparation process Including 4 melting, Metamorphism treatment, casting, heat treatment steps, wherein using the method for melting twice, first time melting will for melting Pure iron, steel scrap, ferrosilicon raw material configure alloy, these raw material are added in electric induction furnace or electric arc furnaces after dissolving and are mixed It is even, pour into ingot, slag former silicic acid is added in fusion process in second of melting ingot good using first time smelting and pouring Sodium, smelting temperature are 1530~1550 DEG C, and gas and field trash in sufficiently long time removal aluminium alloy are stood after dissolving.
3. the preparation method of anti-corrosion Ultra-low carbon high silicon iron-base alloy according to claim 2, it is characterised in that described rotten Processing is carried out in ladle, after molten alloy, rare earth ferrosilicon alloy is added at ladle packet bottom, additional amount is processing molten iron Melted molten iron is poured into ladle and is reacted with rare earth ferrosilicon alloy by the 0.5~1.0% of weight, tapping temperature are as follows: 1450 ~1480 DEG C.
4. the preparation method of anti-corrosion Ultra-low carbon high silicon iron-base alloy according to claim 2, it is characterised in that the casting It is to be poured the molten iron after Metamorphism treatment using Resin sand assembled core mold cast form using the enclosed running gate system that flows slowly For note in the type chamber of resin bonded sand mould, pouring temperature is 1380~1420 DEG C.
5. the preparation method of anti-corrosion Ultra-low carbon high silicon iron-base alloy according to claim 2, it is characterised in that at the heat Reason is using red processing of bringing down a fever after casting, and after casting solidification shapes 0.5h-1h, hot charging enters preparatory heating in the state of not unpacking Into 700~850 DEG C of heat-treatment furnaces, after heat preservation 2-3 hours, 50 DEG C are as cold as with 5-8 DEG C/h of cooling velocity furnace and is come out of the stove.
CN201910267379.5A 2019-04-03 2019-04-03 A kind of anti-corrosion Ultra-low carbon high silicon iron-base alloy and preparation method thereof Pending CN110042302A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115786803A (en) * 2022-12-15 2023-03-14 安徽信息工程学院 High-silicon corrosion-resistant cast iron and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1036790A1 (en) * 1980-04-01 1983-08-23 Рубежанский филиал Ворошиловградского машиностроительного института Corrosion resistant cast iron
CN101122029A (en) * 2007-04-25 2008-02-13 太原钢铁(集团)有限公司 High-silicon cast iron battery lead plate and preparation method thereof
CN104018057A (en) * 2014-06-13 2014-09-03 北京科技大学 Ultra-low carbon ferrite high-silicon iron-based alloy and manufacturing method thereof
CN104043808A (en) * 2014-06-20 2014-09-17 北京科技大学 Copper wire mesh composite high silicon iron base alloy plate electrode and manufacturing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1036790A1 (en) * 1980-04-01 1983-08-23 Рубежанский филиал Ворошиловградского машиностроительного института Corrosion resistant cast iron
CN101122029A (en) * 2007-04-25 2008-02-13 太原钢铁(集团)有限公司 High-silicon cast iron battery lead plate and preparation method thereof
CN104018057A (en) * 2014-06-13 2014-09-03 北京科技大学 Ultra-low carbon ferrite high-silicon iron-based alloy and manufacturing method thereof
CN104043808A (en) * 2014-06-20 2014-09-17 北京科技大学 Copper wire mesh composite high silicon iron base alloy plate electrode and manufacturing method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115786803A (en) * 2022-12-15 2023-03-14 安徽信息工程学院 High-silicon corrosion-resistant cast iron and preparation method thereof

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Application publication date: 20190723