CN103194562A - Nodulizing agent for nodular cast iron and preparation method of nodulizing agent - Google Patents
Nodulizing agent for nodular cast iron and preparation method of nodulizing agent Download PDFInfo
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- CN103194562A CN103194562A CN2013101166315A CN201310116631A CN103194562A CN 103194562 A CN103194562 A CN 103194562A CN 2013101166315 A CN2013101166315 A CN 2013101166315A CN 201310116631 A CN201310116631 A CN 201310116631A CN 103194562 A CN103194562 A CN 103194562A
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Abstract
The invention discloses a nodulizing agent for a nodular cast iron and a preparation method of the nodulizing agent, mainly solving the problem that the soil price is increasingly raised, therefore the preparation cost of a rare earth magnesium based nodulizing agent is greatly increased. The nodulizing agent for the nodular cast iron comprises the following components by mass percent: 7 to 9% of Mg, 35 to 40% of Si, 3 to 5% of RE, 1 to 1.9% of Ca, 1 to 2% of Ba, 1 to 2% of Sr, and the balance of Fe. The preparation method of the nodulizing agent for the nodular cast iron comprises the following steps of: (1) preparing raw materials: preparing the raw materials according to the mass percent of the nodulizing agent for the nodular cast iron; (2) filling into a furnace through a layered filling way; (3) melting; (4) pouring and cooling: pouring and cooling the molten alloy solution into an ingot mould; and (5) granulating. According to the nodulizing agent for the nodular cast iron and the preparation method of the nodulizing agent, the Ca element, Ba element and Sr element are adopted to replace the rare earth elements, therefore, the amount of used rare earths is increased in the premise that the nodulizing effect is ensured, and the production cost of the nodulizing agent is decreased.
Description
Technical field
The present invention relates to the Manufacturing Technology of Nodular Cast Iron field, especially a kind of spheroidal graphite cast iron nodulizing agent and preparation method thereof.
Background technology
Spheroidal graphite cast iron is a kind ofly to obtain globular graphite by nodularization and inoculation, improves the iron machine performance effectively, particularly improves plasticity and toughness, thereby obtains than carbon steel high intensity also.The spheroidal graphite cast iron mechanical property is close to steel, and wear resistance, damping property are better than steel, just is being based on its excellent performance, has been successfully used to some stressed complexity, the part that intensity, toughness, wear resistance are had relatively high expectations.So-called " with iron for steel " mainly refers to spheroidal graphite cast iron.China's spheroidal graphite cast iron output had reached 1,400 ten thousand tons in 2012, and its market requirement increases year by year.
Nodulizing agent is the critical material that spheroidal graphite cast iron is produced, and its tissue to magnesium iron, performance and stable processing technique, production cost etc. have great effect.Although the kind of nodulizing agent is a lot, use maximum still rare earth magnesium class nodulizing agents at home at present both at home and abroad.
Nodulizing agent mainly contains following a few class both at home and abroad at present: (1) pure magnesium: this is external nodulizing agent commonly used, and pressure of magnesium adding is produced magnesium iron, and domestic production equipment is difficult to control, and domestic application is fewer.(2) copper magnesium, nickel magnesium: early stage this alloy that uses of China, but cost height, the copper and mickel accumulation is difficult to control in the foundry returns, causes toughness to descend.(3) Si-Mg-Fe alloy: this nodulizing agent is for the treatment of sulphur and the lower molten iron of tension-active element content, pours into a mould the foundry goods of medium section thickness.Want at home at present in enormous quantities will to produce certain contradiction with working condition and the materials procurement of China foundry enterprise for the manufacture of spheroidal graphite cast iron.(4) rare earth magnesium class alloy: comprise alloys such as rare earth silicon and magnesium, rare earth calcium magnesium, rare earth copper magnesium, be that China engineering technical personnel base oneself upon China's reality, rare earth magnesium class series alloy nodulizing agent in the early sixties development, they combine the relative merits of various nodularization elements, especially rare-earth, Mg, Ca alloy, be the main nodulizing agent that present domestic application has a large capacity and a wide range, thereby walked out the spheroidal graphite cast iron manufacturing technology road of a suitable China's national situation.But because this kind nodulizing agent is to rare earth dependency degree height, constantly under the soaring situation, its preparation cost also significantly increases in current rare earth price.
Summary of the invention
The object of the present invention is to provide a kind of spheroidal graphite cast iron nodulizing agent and preparation method thereof, this spheroidal graphite cast iron uses nodulizing agent and preparation method thereof on the basis of analysing in depth rare earth element mechanism of action in spheroidal graphite cast iron is produced, add Ca, Ba, Sr element substitution rare earth element, thereby under the prerequisite that guarantees the nodularization effect, reduce the consumption of rare earth, reduce the production cost of nodulizing agent.
A kind of spheroidal graphite cast iron nodulizing agent is characterized in that, described spheroidal graphite cast iron with chemical ingredients and the mass percent of nodulizing agent is: Mg:7%～9%, and Si:35%～40%, RE:3%～5%, Ca:1%～1.9%, Ba:1%～2%, Sr:1%～2%, surplus is Fe.
Preferably, described nodulizing agent particle diameter is 3～8mm.
All right, described nodulizing agent particle diameter is 0.2～0.7mm.
The present invention also provides the preparation method of a kind of spheroidal graphite cast iron with nodulizing agent, it is characterized in that, may further comprise the steps:
(1) prepare raw material: get corresponding raw material by above-mentioned spheroidal graphite cast iron with the chemical ingredients of nodulizing agent and mass percent and allocate, wherein, the Mg element is selected from MAG block, and the Si element is selected from ferrosilicon, foundry return and rare earth ferrosilicon alloy with other elements;
(2) shove charge: the mode that adopts the layering shove charge, elder generation occupies one deck with rare earth ferrosilicon alloy at furnace bottom, and most ferrosilicon is covered above the rare earth ferrosilicon alloy, MAG block is gathered to be placed on above the ferrosilicon mid-way then, at last foundry return is covered above the MAG block, and fill up around the MAG block;
(3) fusing: rapid heating, in the heat-processed, plug in pricker furnace charge end face with drill rod, the ferrosilicon for the treatment of the MAG block surface coverage is shiny red and when beginning to adhere to drill rod, stirs, if stir back alloy thickness, then continue to heat up at a small amount of ferrosilicon of surface coverage, stir, operation according to this is until alloy liquation thickness and all join in the stove remaining ferrosilicon several times no longer;
(4) cast cooling: the alloy liquation after will melting is poured into a mould cooling in ingot mould;
(5) granulate: the alloy through overcooling in the step (4) is carried out the fragmentation granulation.
Preferably, the ingot mould wall thickness of described ingot mould: ingot mould thickness 〉=1:1.
Preferably, force cooling before described ingot mould uses.
Main chemical elements symbol and title that the present invention uses are explained as follows: Mg: magnesium, Si: silicon, Ca: calcium, Ba: barium, Sr: strontium, Fe: iron, Re: full name is RareEarth, refer to rare earth element, rare earth element be in the periodic table of elements lanthanon and with the closely-related scandium of lanthanon (Sc) element and yttrium (Y) element.
Spheroidal graphite cast iron is that composition by each alloying element determines that chemical ingredients of the present invention is to determine like this with the performance of nodulizing agent:
Magnesium: be argenteous metal, soft and high resilience, oxidation and cover with the oxide film of one deck densification easily in air.The chemical property of magnesium is very active, and the most of components in energy and the molten iron react, and forms MgC
2, Mg
2C
3, Mg
2Si, Mg
3P
2, MgS, MgO, Mg
3N
2Deng compound and emit a large amount of heat, the melting point compound height of formation, density is separated with molten iron easily also much smaller than iron, reaches the purpose of purifying molten iron.Magnesium facilitates the formation of globular graphite relevant with the effect of its deoxidation desulfuration, because the boiling point of magnesium is low, adds evaporation rapidly behind the molten iron, causes violent the seething of molten iron, the gas in the molten iron, is mingled with to the diffusion of magnesium steam bubble or absorption and is taken out of molten iron, and molten iron greatly purifies.Although from thermodynamic condition, the avidity of magnesium and oxygen, sulphur will be inferior to calcium and cerium, because the molten iron that the magnesium evaporation causes seethe the dynamic conditions that has improved magnesium deoxidation desulfuration greatly, thereby the actual deoxidation desulfuration ability of magnesium in molten iron be greater than calcium, cerium.The free sulphur of molten iron after magnesium is handled, the content of oxygen reduce greatly, and this plays an important role to obtaining globular graphite.Segregation is arranged in the tendency of graphite in the process that magnesium solidifies in molten iron, when its residual quantity in molten iron surpassed 0.035%, graphite just can nodularization, when the magnesium residual quantity surpasses 0.07%, part magnesium segregation is in crystal boundary, and with carbon, phosphorus etc. in the crystal boundary thermopositive reaction takes place, and generates MgC
2, Mg
2C
3, Mg
3P
2More for a long time, the intergranular carbide increases Deng, residual magnesium amount.
Calcium: belong to alkaline-earth metal together with magnesium, chemical property is more active than magnesium.See that from thermodynamic condition the deoxidizing capacity of calcium is greater than magnesium and cerium, sweetening power is only second to cerium and greater than magnesium, thereby be fabulous reductor and sweetening agent, but because the boiling point of calcium is higher, under common treatment temp, calcium adds molten iron and does not resemble and produce the effect of significantly seething the magnesium, thereby calcium and oxygen, the effect of sulphur can only take place at the contact interface of calcium and molten iron, reaction is subjected to the dissolving of calcium, the influence of factors such as diffusion and reaction product eliminating, particularly calcium and molten iron effect rear surface are just wrapped up by oxide compound or the sulfide that reaction generates, internal layer calcium and molten iron continuation effect have been hindered, and calcium proportion is little, float easily to molten iron surface scaling loss, thereby the calcium deoxidation, the dynamic conditions of desulfurization is very poor, and the cleaning action of molten iron be can not show a candle to magnesium.The spheroidization of calcium is also not as magnesium, and only calcium just shows stable nodularization effect when handling low-sulfur (S≤0.03%) molten iron.The nodularization element that uses in the industrial production: the spheroidization ability of magnesium is the strongest in magnesium, yttrium, cerium, calcium and other rare earth elements.Next is yttrium, and it requires the high-carbon hypereutectic composition, and the anti-ageing ability of moving back of yttrium is strong.The spheroidization ability of cerium is poor slightly, and it requires hypereutectic composition, and the immunity from interference of cerium is very strong.The spheroidization ability of calcium is relatively poor, and it requires low-sulfur molten iron, and it is less to handle back magnesium iron chilling tendency.Yttrium, cerium, calcium all require to handle under comparatively high temps, reacting balance, but reacting dynamics condition is relatively poor, especially calcium.Therefore, these several nodularization elements have their own characteristics each.For performance strong point separately, remedy its weakness, can adopt the composite nodulizer that contains magnesium, calcium and other nodularization elements.
Rare earth: judge according to the negative value of standard free energy of formation, rare earth the easiest with molten iron in the oxidation symphysis become oxide compound, secondly will form oxysulfide, the compound of rare earth and arsenic, lead, antimony etc. for another example, rare earth nitride is the formation carbide at last.Certainly rare earth in molten iron with the reaction of these elements except with this temperature under free energy of formation have outside the Pass, also relevant with each constituent content, reaction conditions.In molten iron, to form the less compound of free energy negative value, just need to increase rare earth adding quantity.Can form compounds with oxygen, sulphur, nitrogen, hydrogen etc. because rare earth has good cleaning action rare earth element, but influenced by several factors and present the rule of complexity in the reaction of molten iron middle-weight rare earths and these elements.But rare earth adds in the molten iron and can desulfurization degas in general, and especially when handling with magnesium-rare earth, effect is better.The rare earth oxide standard free energy of formation is much more negative than the oxide compound free energy of formation of iron, manganese, aluminium, magnesium, calcium, and namely the avidity of rare earth and oxygen is extremely strong, and adding in the molten iron to have strong desoxydatoin.But the rare earth oxide fusing point is far above molten iron temperature, and density approaches or surpasses molten iron density, is difficult for overflowing from molten iron.Therefore rare earth can seize oxygen and form rare earth oxide in molten iron, thereby promotes nodularization, but not necessarily reduces the total oxygen in the cast iron, because the total oxygen of measuring with vacuum fusion method also comprises the chemical combination attitude oxygen in the rare earth oxide of not overflowing.The salt that rare earth oxide is lower with forming fusing point and density and effusion molten iron.Have deoxidation effect preferably so add rare earth ferrosilicon alloy or rare earth silicon-calcium alloy.Rare earth magnesium ferrosilicon alloy is added molten iron, because magnesium plays the boiling stirring action, also promote deoxidation.Though rare earth has certain avidity with nitrogen, contains lanthanum in the molten iron, during elements such as cerium, the solubleness of nitrogen can be increased to the nitrogen content that surpasses normal molten iron.This is because rare earth element can absorb nitrogen.Therefore some test shows that rare earth element denitrogenation in molten iron does not become effective, even also slightly nitrogen pick-up.But at this moment nitrogen may be by rare earth chemical combination or absorption.Rare earth element can absorb hydrogen in a large number, and the solubleness of hydrogen in rare earth element is than extremely several thousand times of the high hundred times of solubleness in iron.Rare earth element also can with the hydrogen evolution unstable compounds, it at high temperature decomposes releasing hydrogen gas.After adding rare earth element in the molten iron, total hydrogen content does not reduce, but in process of cooling the hydrogen major part in matrix or the graphite by dissolving that rare earth absorbs.Rare-earth sulfide is compared with magnesium, calcium, the avidity of rare earth element and sulphur is the strongest.Adopt magnesium-rare earth to add in the molten iron, the boiling stirring action of magnesium has improved the dynamic conditions of rare earth desulfurization greatly, and therefore very strong sweetening power is arranged.Because rare earth has distribution and the effect of desulfurization, deoxidation, change nitrogen, hydrogen, has purified molten iron, make and hang down 0.01%～0.02% when the necessary residual magnesium amount of rare-earth magnesium ball iron nodularization is handled than pure magnesium.Rare earth element also reduces molten ductile iron surface film oxide formation temperature.These factors are to improving the mobile of magnesium iron and suppressing loose, slag inclusion and casting flaw such as subsurface porosity produces desirable influence.
Wherein Mg is the strongest nodulizing agent, and it can make the spheroidization of graphite in the molten iron of hypoeutectic, eutectic and hypereutectic composition and have good desulfurization ability to take oxygen.But when only using pure magnesium as nodulizing agent, there is following shortcoming again in it: the boiling point of (1) Mg is lower than molten iron temperature, and Mg directly adds violent boiling in the molten iron, operates that dangerous and molten iron is low to the specific absorption of Mg, nodularization is unstable; (2) pure Mg handle molten steel solidification the time volumetric shrinkage big, the inner shrinkage cavity that forms of foundry goods is difficult thoroughly removes; (3) when micro-tension-active element, just be difficult to make spheroidization of graphite.
Wherein, the Ca element is not only strong deoxidization desulfuration element, also has the effect of auxiliary nodularization; Trace Ba, Sr element promote the graphite pebbles forming core, increase number of graphite ball; RE element such as Ce and La have purifying molten iron and in and the effect of harmful element.
Thulium has the boiling point height, can suppress the advantage of tension-active element interference effect as nodulizing agent; But the rare earth alloy element has following shortcoming again during separately as nodulizing agent: (1) can only nodularization cross brilliant composition molten iron; (2) nodularization graphite rounding not too; (3) rare earth has the effect of aggravation graphite floatation and decaying spheroidisation, rare-earth residual amount＜0.5% o'clock, and graphite shape just obviously worsens (thick, shape degenerates), makes the impelling strength of magnesium iron fall very lowly.Therefore need reasonable disposition Mg element and rare earth elements ratio, and add the Si element and make the magnesium alloy fusing point increase, when in melting master alloy and spheroidizing, magnesium is difficult for scaling loss; Add the proportion that elements such as Ba, Sr increase alloy, prevent that nodulizing agent from floating to the molten iron surface and being burnt, favourable nodularization.
The present invention is low, and rare-earth nodularizer is compared with existing nodulizing agent, has the following advantages:
(1) spheroidal graphite cast iron under the prerequisite that guarantees result of use, has reduced the content of rare earth with nodulizing agent, reduces material cost 30%.
(2) fundamentally solve the spheroidal graphite cast iron industry common problem of the rare earth high flow rate that exists at present, adapting to the cost increase that the rare earth industrial adjustment brings, active response national industry policy.
(3) nodulizing agent of the present invention does not contain expensive alloy element such as molybdenum, nickel, low production cost.
(4) nodulizing agent usage quantity of the present invention is low, can reach nodularization effect preferably.
(5) spheroidal graphite cast iron tensile strength, yield strength, unit elongation, the hardness of using nodulizing agent of the present invention to prepare is higher, and nodulizing grade can reach 2 grades, and the nodularization number can reach 200/mm
2More than.
Description of drawings
Fig. 1 is nodularization metallograph (100 *);
Fig. 2 is matrix metallograph (100 *).
Embodiment
A kind of spheroidal graphite cast iron nodulizing agent, described spheroidal graphite cast iron with the mass percent of nodulizing agent is: Mg:7%～9%, Si:35%～40%, RE:3%～5%, Ca:1%～1.9%, Ba:1%～2%, Sr:1%～2%, surplus is Fe.Described nodulizing agent particle diameter is 3～8mm or 0.2～0.7mm.
The above-mentioned spheroidal graphite cast iron preparation method of nodulizing agent may further comprise the steps:
(1) prepare raw material: by the mass percent proportioning raw material of above-mentioned spheroidal graphite cast iron with nodulizing agent, wherein, the Mg element is selected from MAG block, and Si element and other elements are selected from ferrosilicon, foundry return and rare earth ferrosilicon alloy.
(2) shove charge: the mode that adopts the layering shove charge, earlier rare earth ferrosilicon alloy is occupied one deck at furnace bottom, ferrosilicon with 55%～60% covers above the rare earth ferrosilicon alloy, then MAG block is gathered and be placed on above the ferrosilicon mid-way, at last foundry return and 35%～40% is covered above the MAG block, and fill up around the MAG block.
(3) fusing: rapid heating, in the heat-processed, plug in pricker furnace charge end face with drill rod, the ferrosilicon for the treatment of the MAG block surface coverage is shiny red and when beginning to adhere to drill rod, stirs, if stir back alloy thickness, then continue to heat up at a small amount of ferrosilicon of surface coverage, stir, operation according to this is until alloy liquation thickness and remaining ferrosilicon all joined in the stove several times no longer.
(4) cast cooling: the alloy liquation after will melting is poured into a mould cooling in ingot mould, should force cooling and ingot mould wall thickness when used ingot mould uses continuously before use: ingot mould thickness 〉=1:1.
(5) granulate: the alloy through overcooling in the step (4) is carried out the fragmentation granulation.
Embodiment 1 prescription: spheroidal graphite cast iron with the mass percent of nodulizing agent is: Mg:7%, and Si:40%, RE:5%, Ca:1.6%, Ba:1.4%, Sr:1.4%, surplus is Fe.
Embodiment 2 prescriptions, spheroidal graphite cast iron with the mass percent of nodulizing agent is: Mg:9%, Si:35%, RE:3%, Ca:1%, Ba:1%, Sr:1%, surplus is Fe.
Embodiment 3 prescriptions, spheroidal graphite cast iron with the mass percent of nodulizing agent is: Mg:8%, Si:38%, RE:4%, Ca:1.9%, Ba:2%, Sr:2%, surplus is Fe.
Add above-mentioned nodulizing agent and prepare spheroidal graphite cast iron, add-on is 0.6%.This spheroidal graphite cast iron is carried out metallographic examination and measuring mechanical property, the metallographic examination result as shown in Figure 1 and Figure 2, the nodularization number can reach 200/mm
2More than; According to metallic substance tensile test at room temperature method GB/T228-2002, carry out mechanicl test, the result is as shown in table 1 below.
Table 1 mechanicl test result
Claims (6)
1. a spheroidal graphite cast iron nodulizing agent is characterized in that, described spheroidal graphite cast iron with chemical ingredients and the mass percent of nodulizing agent is: Mg:7%～9%, and Si:35%～40%, RE:3%～5%, Ca:1%～1.9%, Ba:1%～2%, Sr:1%～2%, surplus is Fe.
2. a kind of spheroidal graphite cast iron nodulizing agent according to claim 1 is characterized in that, described nodulizing agent particle diameter is 3～8mm.
3. a kind of spheroidal graphite cast iron nodulizing agent according to claim 1 is characterized in that, described nodulizing agent particle diameter is 0.2～0.7mm.
4. it is characterized in that with the preparation method of nodulizing agent as any described spheroidal graphite cast iron in the claim 1～3, may further comprise the steps:
(1) prepare raw material: get corresponding raw material by above-mentioned spheroidal graphite cast iron with the chemical ingredients of nodulizing agent and mass percent and allocate, wherein, the Mg element is selected from MAG block, and the Si element is selected from ferrosilicon, foundry return and rare earth ferrosilicon alloy with other elements;
(2) shove charge: the mode that adopts the layering shove charge, earlier rare earth ferrosilicon alloy is occupied one deck at furnace bottom, ferrosilicon with 55%～60% covers above the rare earth ferrosilicon alloy, then MAG block is gathered and be placed on above the ferrosilicon mid-way, at last foundry return and 35%～40% is covered above the MAG block, and fill up around the MAG block;
(3) fusing: rapid heating, in the heat-processed, plug in pricker furnace charge end face with drill rod, the ferrosilicon for the treatment of the MAG block surface coverage is shiny red and when beginning to adhere to drill rod, stirs, if stir back alloy thickness, then continue to heat up at a small amount of ferrosilicon of surface coverage, stir, operation according to this is until alloy liquation thickness and all join in the stove remaining ferrosilicon several times no longer;
(4) cast cooling: the alloy liquation after will melting is poured into a mould cooling in ingot mould;
(5) granulate: the alloy through overcooling in the step (4) is carried out the fragmentation granulation.
5. a kind of spheroidal graphite cast iron according to claim 4 is characterized in that the ingot mould wall thickness of described ingot mould: ingot mould thickness 〉=1:1 with the preparation method of nodulizing agent.
6. a kind of spheroidal graphite cast iron according to claim 5 is characterized in that with the preparation method of nodulizing agent, forces cooling before described ingot mould uses.
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Cited By (4)
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| CN106755724A (en) * | 2016-12-28 | 2017-05-31 | 南京浦江合金材料股份有限公司 | It is a kind of to be applied to the smelting technology that 3 tons of intermediate frequency furnaces produce nodulizer |
| CN109957633A (en) * | 2019-03-21 | 2019-07-02 | 南京镝峰复合材料有限公司 | Nodulizer with protective film |
| CN109957632A (en) * | 2019-03-21 | 2019-07-02 | 南京镝峰复合材料有限公司 | A kind of nodulizer |
| CN111020097A (en) * | 2019-12-26 | 2020-04-17 | 陈红喜 | Preparation method of low-magnesium nodulizer |
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| CN109957632A (en) * | 2019-03-21 | 2019-07-02 | 南京镝峰复合材料有限公司 | A kind of nodulizer |
| CN111020097A (en) * | 2019-12-26 | 2020-04-17 | 陈红喜 | Preparation method of low-magnesium nodulizer |
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