CN1084579A - Polycompound nodulizer for nodular cast iron - Google Patents
Polycompound nodulizer for nodular cast iron Download PDFInfo
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Abstract
The present invention proposes a kind of polycompound nodulizer that is used for spheroidal graphite cast iron, contain 0.1 to 20% magnesium, less than 15% rare earth, less than 90% silicon, less than 10% calcium, less than 10% strontium, less than 30% barium, less than 15% zirconium, less than 20% titanium, less than 10% bismuth, less than 20% antimony, less than 30% tin, less than the mixture of 15% aluminium or they and iron, this nodulizing agent has stronger living nuclear capability and the anti-decaying spheroidisation ability of breeding certainly, can significantly increase number of graphite ball, improve nodulizing grade, reduce chilling tendency, be specially adapted to the production of as-cast ball iron.
Description
The invention relates to the production of cast iron, is exactly production and nodulizing agent thereof about spheroidal graphite cast iron more precisely.
Cast iron generally melts in cupola furnace or induction melting furnace.Cast iron generally contains the carbon of about 2-4%, and the form of carbon in cast iron has very remarkable influence to its performance, if the carbon in the cast iron exists with the form of iron carbide, cast iron is just hard and crisp, is called white cast iron; If carbon is got the graphite state, but cast iron is called grey cast iron with regard to mechanical workout.
Graphite can be flaky in cast iron, and is vermiform, and forms such as group's globular exist, and when graphite existed with balled form, cast iron had best intensity and toughness plasticity, was called spheroidal graphite cast iron.
The intensity of spheroidal graphite cast iron and toughness plasticity and cast steel are similar, but production technique is easier than cast steel, and it is with low cost, therefore the range of application of spheroidal graphite cast iron is in continuous expansion, it is amazing as the tempo of new engineering material, whole world spheroidal graphite cast iron ultimate production surpasses 1,000 ten thousand tons, estimates to reach 2,000 ten thousand tons by 2000.
The principal element that influences the performance of spheroidal graphite cast iron is spheroidization of graphite grade, sphere diameter size and matrix and crystal boundary state.The approach of control spheroidal graphite cast iron performance mainly is the adjustment Chemical Composition, selects nodulizing agent, nucleating agent and nodularization, inoculation process, thermal treatment process for use in the production.Adding nodulizing agent-be spheroidizing in iron liquid is the method that obtains globular graphite in the industrial production; It is the method for adjusting matrix that nodular iron casting is heat-treated.
The object of the present invention is to provide a kind of new spheroidal graphite cast iron nodulizing agent, this nodulizing agent is except that containing conventional nodularization element M g, Re, also contain multiple auxiliary nodularization and give birth to nuclear element, have stronger living nuclear capability and the anti-decaying spheroidisation ability of breeding certainly, prevent graphite morphology, reduce chilling tendency, significantly increase number of graphite ball, improve nodulizing grade.Overcome the deficiency of prior art.
Basic design of the present invention is based on following result of study proposition.
Magnesium can make cast iron obtain nodularization fully and uniformly because of it has intensive deoxidization desulfuration ability and strong spheroidization ability, and nearly all practical nodulizing agent all contains magnesium.Magnesium is that the main effect of nodulizing agent middle-weight rare earths element has 3 points: the deleterious effect of 1, eliminating interference element such as titanium, antimony, arsenic etc.; 2, cleaning action; 3, replenish spheroidization.Facts have proved that the rare earth element in the magnesium that spheroidization is very strong, the rare earth element, particularly nodulizing agent adds in the molten iron, at first is to consume in deoxidation, desulfurization and in and on the interference element.Therefore, the content of magnesium, rare earth should be consistent with oxygen, sulphur and interference element in the base iron in the nodulizing agent, could guarantee that nodularization is good, and general Mg content should be in 0.1-20%(weight), content of rare earth should reach 0-15%(weight).Further Mg content should be 1-15%(weight), be preferably in 2-10%(weight) between.
Rare earth, magnesium elements are strong carbide forming elements, have very strong chilling tendency.Surpass required rare earth, the magnesium of nodularization and in magnesium iron, play alloying action, will cause the generation of primary carbide.Excessive rare earth element not only increases chilling tendency, increase and stable perlite, and the graphite that causes making a variation forms in big section.Therefore, rare earth, the magnesium elements content in nodulizing agent is also unsuitable too high, and especially in the production of large-section magnesium iron and as-cast ferrite ductile iron, the content of rare earth must strict be controlled, and content of rare earth is preferably less than 12%(weight); And content of rare earth is less than 10%(weight) time, best results.
Silicon, calcium, aluminium are the conventional elements in the well-known nodulizing agent, and content range of the present invention is respectively less than 90%(weight) silicon, less than 10%(weight) calcium, less than 15%(weight) aluminium.And further silicone content should be less than 70%, and good industrial nodulizing agent contains has an appointment less than 50% silicon (weight).
In order to obtain good nodularization effect, prevent decaying spheroidisation, except that should strengthening in the ductile iron production process the inoculation, nearest research work shows that it is very useful having from the nodulizing agent that breeds ability.In the nodulizing agent that contains calcium, aluminium, add about strontium below 10% and can obtain to have the nodulizing agent that breeds ability certainly.This nodulizing agent preferably contains the strontium of 0.1-4%, and can obtain better effect with the strontium of 0.4-1%.
Have been found that at present and in the nodulizing agent that contains strontium, add the ability that breeds certainly that zirconium can increase this nodulizing agent.This is to make us surprised and beyond thought because zirconic contain silicon inoculant can not produce with contain strontium contain the same good result of silicon inoculant.
Also very be surprised to find that, added the ability that breeds certainly that titanium also can increase this nodulizing agent to the nodulizing agent that contains strontium.This also is surprising discovery, and is low because the efficiency ratio of titaniferous nucleating agent contains the nucleating agent of strontium, therefore, adds the ability that breeds certainly that titanium should reduce nodulizing agent to the nodulizing agent that contains strontium.But unexpected fully, compete to occur just in time opposite stack efficient.
Also find in addition, in the nodulizing agent that contains strontium, add the ability that breeds certainly that zirconium and titanium can increase this nodulizing agent.This is very surprising and beyond thought.Because the front said, independent zirconic contain silicon inoculant or the simple titaniferous inoculation efficiency that contains silicon inoculant than contain strontium to contain silicon inoculant low.But added zirconium and titanium additives and improved the ability that breeds certainly that contains the strontium nodulizing agent unexpectedly.The content of zirconium of the present invention should be preferably between about 0.1-10% greatly between 0-15%, and adopts the about 0.5-2.5% of zirconium content will obtain best effect.Titanium content of the present invention should be preferably between the 0.1-10% between about 0-20%, can obtain best effect when titanium is approximately 0.3-8%.
The result of research shows, barium not only can reduce the content of magnesium in the nodulizing agent, reduce the fierce degree of reaction, improve processing performance and labor condition, can also make the modification effect of calcium be able to more abundant, long lasting bringing into play, from thermodynamic (al) angle, barium has the tendency of the formation carbide bigger than magnesium on the one hand, has the deoxidation stronger than magnesium, sweetening power simultaneously again.Because stable carbide elements such as barium and oxygen, sulphur, nitrogen generate compound, have again to promote ferritic " indirect action ".Therefore, the action rule of barium is very complicated, and is closely related with its content range.According to the present invention, the content of barium should be below 30%, preferably less than 20%, and the best when its content is 0.1-15%.
Antimony and bismuth often are regarded as the harmful element in the magnesium iron, but since the eighties, people find that but these two elements can increase number of graphite ball under the condition that has rare earth to exist, make the graphite pebbles rounding, eliminate or alleviate the distortion of spheroidal graphite in the heavy section casting.The content of bismuth should be less than 10% among the present invention, preferably less than 8%, when bi content 5% when following, effect is better, the content of antimony should further should preferably should be controlled antimony content below 13% less than 15% less than 20%.
Though can contain tin in the nodulizing agent, this is not necessary.Have only when producing pearlitic ductile iron, just allow to contain in the nodulizing agent tin, at this moment, its content should not surpass 30%, preferably tin content is limited in 20%.
When simultaneously adding above-mentioned various element in nodulizing agent, its content is identical with the quantity of a certain element of independent interpolation.Employing does not have special advantage, and can only cause the increase of nodulizing agent cost greater than the constituent content of the present invention regulation, and because the slag inclusion that the interpolation of excessive easy reactive element causes makes foundry goods generation defective.
Can make nodulizing agent of the present invention with the method for any routine with general raw material.After treating that in general silicon-iron bath forms, the material that will be rich in other element with the method for any routine is incorporated in this molten bath together again.Preferably adopt submerged arc furnace, induction melting furnace, vacuum melting furnace or controlled atmosphere smelting furnace to produce silicon-iron bath.Thereafter cast with ordinary method and make melt solidifying.
Use the broken solid nodulizing agent of ordinary method then, it is added in the molten iron easily goes.The nodulizing agent size that is broken depends on nodulizing process, treatment temp and processing iron water amount.
The another kind of method of making this nodulizing agent is, packed in the reaction vessel in various layers of material ground, makes its fusing, and casting is as stated above again solidified and broken.
The matrix alloy of nodulizing agent is preferably used the available silicon-iron of any ordinary method, for example produces the melt of quartzy and scrap iron with ordinary method.Also can be with the silicon-iron that has formed or metallic iron and silicon.
Which kind of matrix alloy this nodulizing agent no matter use, and its silicone content is approximately less than 90%, preferably less than 70%, when silicone content less than 50% the time, will obtain best effect, when making nodulizing agent with silicon-iron-based body alloy, except other all elements, remainder is an iron.
As everyone knows, rare earth, magnesium, calcium, strontium, barium, zirconium etc. all are to be easy to volatilize and the easy element of reaction, during the content of required various elements, must take into account above-mentioned situation in the decision nodulizing agent.In this specification sheets and claims, the percentage ratio of element, except as otherwise noted, the weight percentage in the finished product that all refer to solidify.
Nodulizing agent is preferably formed by the molten mixture of above-mentioned described different components.But also comprise with the form of drying composite or comprise that all green briquettes that do not form the molten mixture composition make nodulizing agent of the present invention.
With any ordinary method nodulizing agent is incorporated in the cast iron.The general ladle bottom pouring process that adopts can obtain satisfied effect.The nodulizing agent quantity of adding can be according to factors vary such as melting method, base iron composition, treatment temp, foundry goods size, the magnesium iron trades mark.When adopting ladle bottom pouring process, handle the nodulizing agent that molten iron per ton need add about 0.8-2.5% and can obtain satisfied effect.
Use nodulizing agent of the present invention, be equipped with suitable production technique, can obtain to meet the nodular iron casting of trade mark requirement, save thermal treatment man-hour and expense in as cast condition.
The following examples are in order to explanation the present invention.
Embodiment 1:
A kind of method of nodulizing agent of the present invention is made in the present embodiment explanation.
Used various starting material hierarchically are put into according to ratio requirement in the cupola well of induction heater, and all compositions get by common material source.Under covering at the part argon gas, this molten bath remains on alap temperature and the fusing said composition is minimized down in oxidational losses.Resulting molten mixture cast, solidify, fragmentation.
Various composition quantity in the nodulizing agent must control, so that make it accord with the scope of the present invention's regulation, can accomplish this point with general method, make the nodulizing agent that the present invention suits thus.
Embodiment 2:
The another kind of method of this nodulizing agent is made in the present embodiment explanation.
According to a conventional method, enter quartz, scrap iron and carbon source in the submerged arc furnace generation ferrosilicon that reacts, wherein silicone content be the fused solution gross weight 90% in, with ordinary method the calcium amount in silicon-iron is adjusted to below 10%, again used other various starting material are added in this fused solution according to ratio requirement, as embodiment 1, adjust composition again, cast, solidify, fragmentation.
Can make the nodulizing agent that the present invention suits thus.
Embodiment 3:
Present embodiment illustrates with nodulizing agent production ultra-thin-wall cast condition ductile iron of the present invention, and compares with a kind of common used in industry nodulizing agent.
Make furnace charge with Hebei province Xingtai Iron and Steel Works pig iron and A3 steel, insufficient Si regulates in stove with 75Si Fe, and cast iron ingredient is:
C-3.95 Si-1.33 Mn-0.114
S-0.059 P-0.06
The molten iron acid high-frequency melting furnace of 60Kg, the base iron composition is:
C-3.7～3.9 Si-1.7～2.0 Mn-≤0.3
S≤0.07 P≤0.07
When molten iron was warmed up to 1500-1520 ℃, employing was poured method and is carried out spheroidizing.The nodulizing agent add-on is that 1.2-2.2%(accounts for molten iron heavily, down together), adding 0.4% the 75Si Fe insulating covering agent as nodulizing agent in the bag, is that 80 purpose 75Si Fe subcontract and breed the back and adopt clay-bonded sand wet type cast test piece as shown in Figure 1 with 0.1% granularity, in order to mensuration amount of deflection and hardness again.
Adopt polycompound nodulizer of the present invention and the most general domestic packet header Mg8Re5 nodulizing agent to compare in the test respectively, the result is as follows:
| Test piece wall thickness (mm) | Span (mm) | Amount of deflection (mm) | HB | ||
| Nodulizing agent of the present invention | Mg8Re5 | Nodulizing agent of the present invention | Mg8Re5 | ||
| 3 | 60 | 3.5 | 2 | 217 | 212 |
| 5 | 100 | 5.5 | 3.5 | 210 | 262 |
| 8 | 200 | 19 | 11.5 | 183 | 262 |
| 10 | 200 | 18 | 8 | 183 | 241 |
The result shows that polycompound nodulizer of the present invention is compared with present the most general domestic packet header Mg8Re5 nodulizing agent, is specially adapted to make the ultra-thin-wall as-cast ferrite ductile iron.
Embodiment 4:
The present embodiment explanation is produced cast condition ductile iron with polycompound nodulizer of the present invention and is contained the rare earth ferrosilicomagnesium of same amount but do not contain other micro-nodulizing agent and compares.
Furnace charge is Benxi Z15 pig iron, foundry returns and steel scrap, and control base iron composition is:
C-3.6～3.9 Si-1.05～1.75 Mn-0.3～0.6 S＜0.03 P＜0.07
Molten iron is founded in electric arc furnace or acid medium-frequency induction furnace, spheroidization treatment temperature is 1430-1480 ℃, adopt ladle bottom pouring process, the nodulizing agent of 1.2-2.15% is placed on bottom, bag hole, last covering 75Si Fe 0.4%, loam cake perlite or magnesium iron bits or steel sheet, the 75Si Fe with 0.154-0.20% during cast carries out current-following inoculation, and the gained result is as follows:
| Interventions Requested | Casting section thickness mm | Polycompound nodulizer of the present invention | With the content rare earth-Si-Fe-Mg |
| Graphite pebbles several/mm 2 | 3 | 3000 | 1148 |
| 5 | 2099 | 960 | |
| 8 | 1502 | 1002 | |
| 15 | 1376 | 830 | |
| 25 | 847 | 598 | |
| Ferrite content % | 3 | 25 | 6.75 |
| 5 | 30 | 6.5 | |
| 8 | 38.13 | 12.0 | |
| 15 | 49.38 | 29.2 | |
| 25 | 69.17 | 48 | |
| Carburizing scale of construction % | 3 | 0 | 13.55 |
| 5 | 0 | 12.75 | |
| 8 | 0 | 6.6 | |
| 15 | 0 | 2.6 | |
| 25 | 0 | 0 |
The result shows, under same working condition, polycompound nodulizer of the present invention is having remarkable advantages than the rare earth ferrosilicomagnesium nodulizing agent that contains same quantity that does not contain trace element aspect living nuclear capability, the minimizing chilling tendency, can significantly increase number of graphite ball, reduce cementite content, increase ferrite quantity, reduce sensitivity profile, improve the casting section homogeneity.
Embodiment 5:
The present embodiment explanation is produced the extra-large cross-section casting ferrite with nodular cast iron with polycompound nodulizer of the present invention.
Use Wuhan Iron and Steel Company's pig iron, melting in the water jacket cupola outside 10t/hr., control base iron composition is 3.36-4.10%C, 0.7-1.2%Si ,≤0.2%Mn, ≤ 0.07%P, ≤ 0.07%S, the ladle bottom pouring process spheroidizing is adopted in tapping temperature 〉=1400 ℃, adding nodulizing agent of the present invention is 1.6-2.1%, and controlling whole silicon amount is 1.6-2.2%.Casting weight is the 5-8 ton in the carbon sand dry type, and wall thickness is a 270-425mm extra-large cross-section magnesium iron spare, and as-cast characteristic reaches the requirement of the QT400-18 trade mark, and 45% as cast condition unit elongation δ 〉=20% is arranged, and the highest δ value reaches 26%.Prove that nodulizing agent of the present invention has good anti-decaying spheroidisation ability, can prevent graphite morphology, solved and produced the insoluble key problem in technology of extra-large cross-section magnesium iron spare in the world wide.
Self-evident, the most preferred embodiment of lifting for explanation in the literary composition is all changes and the improvement that is used for comprising most preferred embodiment of the present invention, and this does not exceed scope of the present invention.
Description of drawings:
Fig. 1 is that embodiment 3 is in order to measure the test piece synoptic diagram of amount of deflection and hardness.
1 is cast gate among Fig. 1, and 2 is cross gate, and 3 are test piece, test piece length and width, thick parameter unit (mm).
Claims (14)
1, a kind of polycompound nodulizer that is used for spheroidal graphite cast iron comprises: magnesium, rare earth, silicon, approximately less than 10% (weight) calcium and one or more being selected from by independent strontium, barium, zirconium, titanium, bismuth, antimony, tin, aluminium or their additive in conjunction with the series of being formed.
2, nodulizing agent according to claim 1, wherein Mg content is about 0.1-20%(weight), content of rare earth is approximately less than 15%(weight), silicone content is approximately less than 90%(weight), content of strontium is approximately less than 10%(weight), barium content is approximately less than 30%(weight), zirconium content is approximately less than 15%(weight), titanium content is approximately less than 20%(weight), bi content is approximately less than 10%(weight), antimony content is approximately less than 20%(weight), tin content is approximately less than 30%(weight), aluminium content is approximately less than 15%(weight).
3, nodulizing agent according to claim 2, wherein content of strontium is about 0.4-1%(weight), barium content is about 0.1-15%(weight), zirconium content is about 0.5-2.5%(weight), titanium content is about 0.3-8%(weight), bi content is approximately less than 7%(weight), antimony content is approximately less than 13%(weight).
4, a kind of polycompound nodulizer that is used for spheroidal graphite cast iron comprises: about 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, approximately less than 90%(weight) silicon, approximately less than 10%(weight) calcium, approximately less than 10%(weight) strontium, approximately less than 30%(weight) barium, and approximately less than 15%(weight) zirconium, approximately less than 10%(weight) bismuth, approximately less than 15%(weight) aluminium.
5, a kind of polycompound nodulizer that is used for spheroidal graphite cast iron comprises: about 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, approximately less than 90%(weight) silicon, approximately less than 10%(weight) calcium, approximately less than 30%(weight) barium, approximately less than 10%(weight) bismuth, approximately less than 15%(weight) aluminium.
6, a kind of polycompound nodulizer that is used for cast iron comprises: about 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, and approximately less than 90%(weight) silicon, approximately less than 10%(weight) calcium, and approximately less than 10%(weight) bismuth.
7, a kind of polycompound nodulizer that is used for cast iron comprises: about 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, and approximately less than 90%(weight) silicon, approximately less than 10%(weight) calcium, and approximately less than 30%(weight) barium.
8, a kind of polycompound nodulizer that is used for cast iron comprises: about 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, approximately less than 90%(weight) silicon, approximately less than 10%(weight) calcium, approximately less than 10%(weight) strontium, and approximately less than 15%(weight) zirconium, approximately less than 20%(weight) titanium, approximately less than 20%(weight) antimony, approximately less than 30%(weight) tin, and approximately less than 15%(weight) aluminium.
9, a kind of polycompound nodulizer that is used for cast iron comprises, about 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, approximately less than 60%(weight) silicon, approximately less than 5%(weight) calcium, approximately less than 20%(weight) titanium, and approximately less than 20%(weight) antimony, approximately less than 30%(weight) tin, approximately less than 15%(weight) aluminium.
10, a kind of polycompound nodulizer that is used for cast iron comprises, about 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, approximately less than 60%(weight) silicon, approximately less than 5%(weight) calcium, approximately less than 20%(weight) titanium, approximately less than 20%(weight) antimony, and approximately less than 30%(weight) tin.
11, a kind of polycompound nodulizer that is used for cast iron comprises, approximately 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, and approximately less than 60%(weight) silicon, approximately less than 5%(weight) calcium, and approximately less than 20%(weight) antimony.
12, a kind of polycompound nodulizer that is used for cast iron comprises, approximately 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, and approximately less than 60%(weight) silicon, approximately less than 5%(weight) calcium, and approximately less than 20%(weight) titanium.
13, a kind of polycompound nodulizer that is used for cast iron comprises, approximately 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, and approximately less than 60%(weight) silicon, approximately less than 5%(weight) calcium, and approximately less than 30%(weight) tin.
14, a kind of cast iron of handling with composite nodulizer, described nodulizing agent contains: about 0.1-20%(weight) magnesium, approximately less than 15%(weight) rare earth, approximately less than 90%(weight) silicon, approximately less than 10%(weight) calcium, approximately less than 10%(weight) strontium, approximately less than 30%(weight) barium, approximately less than 15%(weight) zirconium, approximately less than 20%(weight) titanium, approximately less than 10%(weight) bismuth, and approximately less than 20%(weight) antimony, approximately less than 30%(weight) tin, approximately less than 15%(weight) aluminium.
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| CN 92111099 CN1036935C (en) | 1992-09-22 | 1992-09-22 | Polycompound nodulizer for nodular cast iron |
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| CN 92111099 CN1036935C (en) | 1992-09-22 | 1992-09-22 | Polycompound nodulizer for nodular cast iron |
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| CN1036935C CN1036935C (en) | 1998-01-07 |
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| CN1069349C (en) * | 1997-04-16 | 2001-08-08 | 由淼 | Double layer granular fire-retardant nodulizer composition and preparation method thereof |
| CN1109117C (en) * | 2000-09-18 | 2003-05-21 | 四川营山铸造材料有限责任公司 | Special nodulizer for nodular cast iron and its production process |
| CN1116429C (en) * | 2000-08-08 | 2003-07-30 | 华中科技大学 | Nodulizer for cored wire |
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- 1992-09-22 CN CN 92111099 patent/CN1036935C/en not_active Expired - Fee Related
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| CN1069349C (en) * | 1997-04-16 | 2001-08-08 | 由淼 | Double layer granular fire-retardant nodulizer composition and preparation method thereof |
| CN1116429C (en) * | 2000-08-08 | 2003-07-30 | 华中科技大学 | Nodulizer for cored wire |
| CN1109117C (en) * | 2000-09-18 | 2003-05-21 | 四川营山铸造材料有限责任公司 | Special nodulizer for nodular cast iron and its production process |
| CN101600668B (en) * | 2006-08-02 | 2013-05-01 | 萨克特本化学有限责任公司 | Titanium-containing additive |
| CN101792846A (en) * | 2010-03-24 | 2010-08-04 | 江西省龙钇重稀土材料有限责任公司 | Rare-earth-containing iron and steel modificator and preparation method thereof |
| CN102827987A (en) * | 2012-09-24 | 2012-12-19 | 芜湖市金贸流体科技股份有限公司 | Spheroidizing agent as well as production method and usage thereof |
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| CN107619988A (en) * | 2017-08-31 | 2018-01-23 | 安徽信息工程学院 | Thin-walled ferrite ductile cast iron inovulant and preparation method thereof |
| CN108251589A (en) * | 2018-01-31 | 2018-07-06 | 重庆卡森科技有限公司 | A kind of novel nothing breeds nodulizer |
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