CN102652967A - Method for manufacturing high-magnesium-alloy solid cored wire - Google Patents
Method for manufacturing high-magnesium-alloy solid cored wire Download PDFInfo
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Abstract
The invention relates to a method for manufacturing a metal solid cored wire with a composite material structure, and particularly relates to a method for manufacturing a high-magnesium-alloy solid cored wire for molten iron spheroidization, and is suitable for the method for manufacturing the high-magnesium alloy solid cored wire with brittle magnesium alloy components. The method is characterized by comprising the following steps of: distributing hard and brittle components in a compound in a continuous matrix of a soft metal component in a form of particles by adopting a particle enhanced metal matrix composite material method, forming a flexible metal wire and wrapping to form the metal solid cored wire for the molten iron spheroidization, namely mixing metal magnesium and calcium particles, magnesium-rare earth alloy powder, industrial silicon powder and the like according to a certain proportion, performing cold-pressing to form a blank, preheating and hot-extruding to form the metal wire, and wrapping by a cold-rolled steel band which is 0.3 or 0.4-millimeter thick on a core coating machine to form the metal cored wire. The treatment cost is greatly reduced, and the spheroidization quality is remarkably improved.
Description
The present invention relates to the used real core spun yarn manufacturing approach of a kind of metal of molten iron spheroidising in the spheroidal graphite cast-iron production process.With coarse grain magnesium powder or crystallization magnesium grain, coarse granule calcium grain or crystalline calcium grain, magnesium-rare earth powder, industrial silica fume is raw material, with above-mentioned raw materials particle or powder for drying, ball mill mixing, is cold-pressed into the base of extruding usefulness.With the powder compact segmentation be heated to high temperature and the insulation make it homogenising, be hot extruded into the wire of microstructure of composite structure then.With this composite wire is core, is overmolding to the real core spun yarn of metal with cold-rolled strip.Core-spun yarn of the present invention is a kind of with brittle metal pulvis heart yearn; Change into the real core spun yarn of flexible metal based composites metal, have that production technology is simple, cost is low, spheroidizing reacion is steady, the absorptivity height of nodularization steady quality, magnesium, the advantages little to the pollution of environment such as forming core inoculation(effect), light and cigarette arranged.
Background technology
Spheroidal graphite cast-iron occupies an important position on material market because its cost performance is high, although in the past few years the steel casting total output descends to some extent, magnesium iron output does not descend.Studied successfully bainite ductile iron the seventies in 20th century and be described as one of significant achievement in the cast iron metallurgy in recent decades, after this Ao-Bei magnesium iron has both high strength, high tenacity and high-wearing feature, is referred to as the 21 century material by people.
Using nodulizer to handle is one of main means that obtain at present magnesium iron.The type of nodulizer comprises magnesium Si system alloy, rare earth magnesium Si system alloy, calcium alloy (Japanese usefulness more), and nickel magnesium is alloy, pure magnesium alloy, rare earth alloy, and usefulness is rare earth magnesium ferrosilicon alloy the most widely in the world.The nodulizer that rare earth uses when being the invention magnesium iron, its discovery has advanced the process of magnesium iron commercial Application.Rare earth can promote the nodularization effect (roundness of nodularization rate and ball) of magnesium alloy, and it has received attention to the effect that prevents the globular graphite distortion in the wall thickness magnesium iron spare, and this also is the one of the main reasons that all comprises rare earth in the domestic and international nodulizer.The rare earth price is high, and chilling tendency is big, and excessive meeting makes graphite abnormal, and oneself does not use separately as nodulizer now, only as auxiliary nodularization element.The calcium magnesium nodulizer mainly is that Japan produces and uses, and content of magnesium changes from 4-28% among the calcium alloy NC5 that produces like Japanese SHIN-ETSU HANTOTAI (SHIN-ETSU), NC10, NC15, NC20, the NC25, but intracellular calcium content change is less, and its excursion is 20-31%; This type of alloy chilling tendency is little, but requires treatment temperature high, and it is big to handle the back quantity of slag.Nickel magnesium alloy in America, all there is application in Europe, the nickel magnesium alloy that U.S. International nickel Co. Ltd. Inco. Ltd. produces is up to 82-85%, wherein Mg, Ca are respectively 13-16, and 20, the 57-61% that nickel is minimum (Mg4.0-4.5% wherein, Ca＜2.5%, Fe32-36%).Ni47-51% in the nickel magnesium alloy that Germany metallochemistry company produces, Mg15-17%, C1.0%, Si28-32%, the surplus Fe of RE1.0%.The advantage of these alloys is than great, reacting balance, and nickel can play alloying action, is characterized in expensive.The microstructure and property of magnesium iron depends on the quality of composition and the crystallization condition and the used nodulizer of cast iron, and the principal element of control magnesium iron quality has the type of the composition of cast iron, used nodulizer, inovulant, adding method and cooling condition etc.The composition of as-cast ferrite ductile iron belongs to little hypereutectic composition, and wherein carbon is high slightly, and is siliceous low slightly, and inovulant silicon amount should be less than 3%, has research to point out that during Si=2.6-2.8%, cast iron has the highest percentage elongation and impact flexibility.Should make S≤0.02%, P≤0.02% in the ferritic spheroidal graphite cast iron.As far as pearlitic ductile iron, manganese can be increased to 0.8-1.0% in the cast iron composition when producing, and some foundry goods is if during as the wearability bent axle, and manganese can be increased to 1.2-1.35%.Produce as-cast pearlitic elemental copper addition greater than 1.8% o'clock; It hinders spheroidization of graphite, but promotes the complete pearliteization of matrix, and copper content should be less than 1.5% in the general magnesium iron; Tin is strong pearlite element; Greater than copper and manganese, but Sn >=1.0% o'clock makes graphite morphology to the influence of hardness for it, so its content should be limited in below 0.08%.
It is extremely important link in spheroidal graphite cast-iron production and the research that molten iron is carried out spheroidising, although it is simple to pour method equipment, and operation easily; Flexibility is strong, and required method content is lower, but flame, flue dust in the spheroidising process are very strong; Work situation is seriously polluted, and the alloy consumption is big, and magnesium absorption rate is on the low side; And the nodularization effect is unstable, is prone to situation such as decaying spheroidisation.Usually, only the ratio of the degree of depth of pack processing and internal diameter be 1.5-2 doubly, the sulfur content of base iron could obtain the recovery rate of best spheroidising effect and the highest magnesium when low.Adopt the graphite cover plate to do the method for covering, obtained obvious effects, the cover plate method is suitable in medium and small foundry enterprise, promoting the use of.Will use special-purpose pressure of magnesium adding bag when pure magnesium alloy is handled, the absorptivity of magnesium is high, but it is very strict to handle safety measure, and application percentage is less in the production.In decades, successfully work out multiple nodulizing process both at home and abroad, still had some new nodulizing process at present among research.
The degree of purity that the focus of Iron and Steel Production is higher, higher uniformity.In order to promote the method progress of Iron and Steel Production, should further improve degree of purity, also to pass through residual inclusion modification, comprise reduce size, form nodularization, disperse etc. is evenly distributed.Produce at most best quality products with minimum cost, the core-spun yarn method is various countries, the world today aspect molten steel and molten iron processing many, the most simple and one of the process means the most rapidly and efficiently and the measure of realizing this goal.The core-spun yarn method appears for the first time in late 1970s, steel is added the core-spun yarn method that calcium is treated to main target; The course of successfully passing by more than 30 year, never experienced by people approve consistently praise highly, promote from being applied to large tracts of land among a small circle, refining, microalloying, alloying and rotten desulfurization, nodularization, inoculated and the alloying of handling molten iron from molten steel ... Etc. a series of variation.This variation and result of development not only make STEELMAKING PRODUCTION that revolutionary transformation has taken place, and are also just bringing into play increasing effect aspect the casting of magnesium iron, wriggle iron and gray iron.So domestic, external spheroidal graphite cast-iron production industry all changes hello a silk method nodularization into from pouring the method nodularization gradually.
The cast iron nodularization core-spun yarn normally powder mixture of multiple material adopts high-quality cold-rolled strip method for coating, processes core-spun yarn, joins the molten iron deep layer through mechanical means, is used for molten steel is carried out refining.Inevitably can bring other oxides that the pulvis core-spun yarn exists into and pollute with powder mixture core-spun yarn processing procedure.The heart yearn pulvis has very big specific area, is prone to oxidation and loses activity, and the rate of recovery reduces.Powder core quality is not easy to detect, and is difficult to guarantee the uniformity of core-spun yarn, and core-spun yarn type nodulizer is that magnesium powder, iron powder are coated in sheet metal or the steel plate, it is sent into fast reach the nodularization purpose in the molten iron, and this nodulizer is more expensive, and equipment investment is big.For example; Producing spheroidal graphite cast-iron with high Mg alloy cored wine is with the common low carbon steel band the high magnesium alloy (the polynary pulvis nodulizer that contains magnesium >=30%) of molten iron to be added to be wrapped up becoming a core-spun yarn with random length, it is injected in the molten iron with certain speed by means of the feeding wire machine of being developed then.Along with the band steel near the continuous fusing the ladle bottom, and the composite nodulizer that is wrapped up is released in the molten iron, through the effect of itself and molten iron, thereby reach the purpose of molten iron being carried out desulfurization and spheroidising.The mode that adopts core-spun yarn in molten iron, to add magnesium has been received good effect, and the utilization rate of magnesium is high, and the nodularization rate is high.But except that the shortcoming that also has iron and steel pulvis core-spun yarn, high Mg alloy cored wine also exists smelts difficulty with the nodularization core-spun yarn of powder coated, and powder production has the risk of blast, and production cost is high.
Developed into real core metal core-spun yarn in nearly 2 years again, be about to wire and process core-spun yarn with the steel band coating.The application of real core metal core-spun yarn processing method for the steady production operation, is improved the quality of products, and reduces production costs, and increases economic efficiency and aspect such as environmental protection all has outstanding advantage.Based on the nodularization good combination property of magnesium, attempt the real core spun yarn of research magnesium metal, still; The vapour pressure of magnesium metal is greatly very high during high temperature; For example in the iron liquid more than 1400 ℃, the vapour pressure of magnesium is about 10 atmospheric pressure, and the formula of can blasting when adding in molten iron reaction causes splash; Therefore, iron liquid is handled very difficulty.For this reason; Adopt at present and mix the nodularization core-spun yarn; Promptly constitute, its essence is to be employed in the peripheral method that increases the powder heat-insulation layer of magnesium silk, slow down the violent gasification degree of magnesium by the inovulant powder of steel band parcel and one or more coating magnesium line of being positioned at the powder layer central area.The method of this compromise is not eliminated the shortcoming of powder packets heart yearn fully.
It has been ripe method that the core-spun yarn method is handled for molten steel, and handling for iron liquid also is a new method that has development potentiality, has begun the new stage of spheriodization process thereof.Because carrying out the desulfurization of iron liquid, nodularization and inoculated in the production of spheroidal graphite cast-iron, the core-spun yarn method neither needs a large amount of capital expenditures; Do not need very big place again; Both effectively simple; Can reduce and eliminate the pollution of processing operation to environment again, therefore enjoy the developing direction of favor, reducing processing cost is the key of promoting.
China is main in the world castings production state; Actively in the Foundry Production of China, research and develop real core metal core-spun yarn method; No matter be to the raising of enterprise product quality and the decline of production cost; Still to the improvement of production environment and the product competitiveness on the market at home and abroad, all be a thing that important economic implications and social effect are arranged.Along with industrial expansion, people are increasingly high to the magnesium iron performance demands.Some once played the nodulizing process of important function in ductile iron production, exposed day by day goes out weak point, demanded urgently these methods are improved, and created the spheronization process that makes new advances, and comprised the real core spun yarn of metal.
Summary of the invention
The objective of the invention is to propose a kind of manufacturing approach that is used for the real core spun yarn of metal of cast iron spheroidising.
The present invention realizes so above purpose, for plastic metal ingredients constitute ratio more the nodulizer prescription, utilize the theory of particles reiforced metal-base composition and manufacturing approach to make high magnesium alloy reality core silk.Guiding theory is that the form of the hard crisp composition in the constituent with particle is distributed in the successive substrates of soft metal component.Promptly be distributed in the hard crisp composition silicon powder particle in the original material in the successive substrates of magnesium and calcium formation.Concrete method is to be cold-pressed into base preheating and be hot extruded into wire again after the mixing such as magnesium metal and calcium particle, magnesium-rare earth alloy powder, industrial silica fume, and this is a kind of wire of metal-base composites institutional framework.Extruding silk annealing in process is to increase plasticity, and is anti-oxidant, adopts the phytic acid aqueous solution of 1% concentration that Passivation Treatment is carried out on extruding silk surface.Flexible high magnesium alloy wire coats with steel band, becomes the real core spun yarn of the metal that is used for the molten iron spheroidising.
The application has analyzed high magnesium alloy particles and has strengthened the basis of metal-base composites institutional framework as the real core silk of nodulizer.The foundation of selecting the nodulizer composition is the spheroidizing of promotion graphite, makes the element of graphite nodule generation or increase that following common property generally arranged: on the element outermost electronic shell one or two valence electron is arranged, inferior internal layer has 8 electronics.This electronic structure makes element and sulphur, oxygen and carbon that stronger affinity arranged, and product is stable, can significantly reduce sulphur and oxygen in the agio; Element solubility in molten iron is low, and remarkable segregation tendency is arranged in the process of setting; Though with carbon certain affinity is arranged, solubility is low in the graphite lattice.Mg, Ce, Re, Ca belong to effective nodularization element.Mg element steam pressure in molten iron is high, and the molten iron Buddhist is risen, and therefore, when magnesium adds molten iron, produce vaporization, and molten iron is seethed.Magnesium elements and sulphur, oxygen have very strong affinity, the molten iron after magnesium is handled, and the content of sulphur and oxygen is all very low.The solubility of calcium in molten iron is very low, and it is through realizing indirectly with oxygen and combining of sulphur to the influence of metal structure.The affinity of calcium and sulphur, oxygen is stronger, effectively desulfurization, deoxidizing capacity, and calcium is very little in the solubility of molten steel.Therefore, the magnesium calcium-silicon of high magnesium is that a kind of multi-functional cast iron nodulizer is formed cooperation.
At present; Molten iron is added three types of high Mg alloy cored wines of magnesium processing aspect injection feeding technology, and pure magnesium powder, 30% magnesium powder and ferrosilicon powder, 25% magnesium alloy powder analyze comparison and how tame plant experiment confirms; Be lower than the core-spun yarn of 28% magnesium content, produce cost and all be higher than the method for pouring.Think that it is suitable selecting the multicomponent alloy of 30%-55% magnesium content.The composition that is based on certain producer's actual verification is Mg:45%; Ca:10%; Si:30%; The actual nodularization of the high mg-si master alloy nodulizer of Re:3% is respond well, its nodulizing grade: the 2-3 level; Graphite size size: 7-8 level; Add the Mg amount: be not more than 0.125%; Not as Si measures: improve 0.6% than pouring method; Residual Mg amount: 0.042-0.045%; Residual Si amount: 0.015-0.018%; Mg effective rate of utilization: 43.59-48.08%; 110 yuan of/ton molten iron of processing cost, comparing the method for pouring is 152-176 unit/ton molten iron.It is few that the nodulizer of this composition is handled the back generation quantity of slag to molten iron, and bits are the dried slag that is prone to remove.The exhaust gas volumn that processing procedure produces is few, and environmental pollution is little, and labor strength is little.
This traditionally high magnesium alloy need be said above-mentioned composition smelting melt-casting earlier by the method for pyrometallurgy, needs to adopt the founding hot conditions of ferroalloy; It is violent that the component high-temperature oxydation adds fashionable burning; Need strict anti-oxidation and blast especially, therefore, the melting cost is quite high.The pulverizing of high mg-si master alloy coagulated mass is pulverized also needs strict security measure, the complexity that the existence of production is suitable.If the alloy powder core-spun yarn of content of magnesium more than 40% developed into real core spun yarn, be processed into that instinct reduces significantly, the quality of spheroidising will have obvious improvement.The application surpasses 50% for plastic metal content in the nodulizer material for this reason, adopts the real core silk of the high mg-si master alloy of metal-base composites manufactured.If the alloy powder core-spun yarn of content of magnesium more than 40% developed into real core spun yarn, be processed into that instinct reduces significantly, the quality of spheroidising will have obvious improvement.The application surpasses 50% for plastic metal content in the nodulizer material for this reason, adopts the real core silk of the high mg-si master alloy of metal-base composites manufactured.
The application makes full use of powder metallurgic method and prepares the achievement in research that boron carbide particles strengthens Al alloy composite.Find that in the research of boron carbide particles enhancing Al alloy composite the composite of manufacturing increases percentage elongation decline with strengthening body burden.Even the annealed condition percentage elongation of the B4Cp/6061Al material of high-volume fractional is still than higher.Composite shows higher percentage elongation under the high strain rate; Grain volume fraction be 40% composite under high strain from the distortion of waist drum shape gradually to failure by shear; Has bigger percentage elongation and plasticity preferably; Grain volume fraction be 45% and 50% composite then from failure by shear to the cleavage fracture, show tangible fragility.Therefore, the experimental result that the particles reiforced metal-base composition of volume fraction below 40% do not destroy in high strain rate, but certain plasticity is arranged like fruit granule, even grain volume fraction is that 50% o'clock composite still has certain plasticity.The plasticity of grain reinforced metal and composite is relevant with the design of composite: brittle particle can not be thick excessively, crosses the thick continuity of destroying matrix, can not be meticulous, cross the gross area that detailed rules and regulations increase the interface, and cause fragility to increase fast; Matrix is thin continuous fiber shape, and it is best microstructure of composite form that particle is beading; In order to obtain continuous soft matrix fiber, the granularity of permission soft metal matrix powder can be bigger, and for example magnesium, calcium primary particles are directly formed by the fragmentation of crystallization ingot.In order to solve the relatively poor problem of mixed-powder pressed compact formability, its plasticity has been carried out big quantity research.In order to obtain superplasticity, normally add suitable heat treatment and obtain fine equi-axed crystal through thermal deformation.Electron microscopic observation finds that aluminum matrix composite crystal grain when superplastic tension rotates around strengthening body, and produces slippage.Strengthen body simultaneously and also participate in cooperating this motion of matrix grain, shown tangible superplasticity flow performance.Aluminum matrix composite is in the superplastic deformation process, except that finding to occur also demonstrating highdensity dislocation configuration a large amount of cavities.In the B4Cp/Al that powder metallurgic method makes, the B4C particle as the disperse of a kind of enhancing body be distributed between the powder particle, itself does not deform.For some aluminum matrix composites, be approximately higher than under the situation of matrix solidus temperature at high strain rate and deformation temperature, material has superplasticity.At this moment, produce thin layer of liquid, distortion is carried out under solid-liquid two-phase coexistent state at intergranular.Shear to realize sliding over each other between intercrystalline and crystal grain and enhancing body through thin layer of liquid, thin layer of liquid is as lubricant, makes that to strengthen between body and matrix grain slip easier, thereby improved percentage elongation.
With coarse grain magnesium powder or crystallization magnesium grain, coarse granule calcium grain or crystalline calcium grain, magnesium-rare earth alloy powder, industrial silica fume raw material, its each component content is: magnesium 55%, calcium 10%, rare earth 3%, silicon 32%.With above-mentioned raw materials particle or powder for drying, ball mill mixing, be cold-pressed into the biscuit of given size.With biscuit segmentation heating, earlier with blank heating to 200 ℃, insulation 1 hour, continue to be warmed up to 500-600 ℃ and be incubated 2 hours again, make it homogenising, be hot extruded into the composite wire then.The be squeezed microstructure influence of silk of the flexibility of extruding silk and the effect of spheroidising is very remarkable, and for example, the continuous filament of flexible substrate minor diameter is given the plasticity of extruding Si Genggao, and brittle particle is distributed in the matrix with beading, and the plasticity of extruding thread is also higher.In order to obtain such tissue, the one, as far as possible component is added with the softest form in the parent material, brittle particle is got middle small grain size; Secondly, extrusion ratio is big more, and it is thread to be more conducive to form minor diameter, and the extruded stock size when general industry is produced is very big, and extruding is all enough big usually, satisfies large extrusion ratio and does not have difficulties.To push silk softening annealing process parameter is 300 ℃ of insulations 1.5 hours; Annealing is come out of the stove when being cooled to about 50-100 ℃, with its phytic acid aqueous solution 5 minutes that soaks 1% concentration into, takes out natural air drying then; The stretch percentage elongation of the extruding silk after the annealing surpasses 3%, and bending ductility is good.At last the cold-rolled strip with 0.3 millimeter or 0.4 millimeters thick is overmolding to real core metal core-spun yarn on bag core machine.
Experimentizing in factory confirms the real core spun yarn of high composite material of magnesium alloy, is to replace pouring method with the target of the real core spun yarn of high composite material of magnesium alloy.800 kilograms of intermediate frequency furnace experiments, it is few to compare the exhaust gas volumn that produces when the method that pours is handled, and environmental pollution is little, and it is few to generate the quantity of slag, is the dried slag that is prone to remove, and labor strength is little.For composition for containing 0.6-0.8%Si, 0.2-0.3%Mn,＜0.03P,＜0.03S, temperature is that 1500 ℃ original molten iron carries out spheroidising, analysis result is: nodulizing grade is the 2-3 level; The graphite size size is the 7-8 level; Add the Mg amount and be not more than 0.12%; Residual Mg amount is 0.04-0.046%; The residual Si amount is 0.016-0.019%; Mg average effective utilization rate surpasses 52%.The nodularization effect meets the index of standard code.
Specific embodiment
Embodiment: the real core spun yarn of high magnesium alloy
With magnesium powder or crystallization magnesium grain, calcium grain or crystalline calcium grain, magnesium-rare earth powder, industrial silica fume is raw material, with above-mentioned raw materials particle or powder for drying and by following ingredient composition: magnesium 55%, calcium 10%, rare earth 3%, silicon 32%.With the raw material ball mill mixing, to be cold-pressed into diameter be 130 millimeters powder cylindrical blank.With powder compact segmentation heating, with blank heating to 200 ℃, insulation 1 hour, the purpose of segmentation heating was to eliminate the elastic after effect of powder compact earlier, and elastic after effect possibly cause the damage of powder base.The low-temperature heat continued is warmed up to 500-600 ℃ and be incubated 2 hours, makes it homogenising, and the mould of the preheating of packing into then is hot extruded into the composite wire that diameter is 12mm.To push 300 ℃ of insulations of silk annealing in 1.5 hours, and come out of the stove when being cooled to 50-100 ℃ of scope, and with the phytic acid aqueous solution of its immersion with 1% concentration, take out natural air drying then, the stretch percentage elongation of the extruding silk after the annealing surpasses 3%, and good crooking ability is arranged.Adopt the cold-rolled strip of 0.4 millimeters thick to be overmolding to real core metal core-spun yarn at last.
The real core spun yarn of the application's high composite material of magnesium alloy replaces the method that pours that molten iron is carried out spheroidising, and the spheroidising post analysis proves, effect is with to pour method suitable.The real core spun yarn manufacturing process of high composite material of magnesium alloy of the present invention is simple, manufacturing cost reduces significantly.Use the application's core-spun yarn to improve molten metal nodularization quality, reduce the spheroidising cost, reduce pollution, realize mechanization, reduce working strength of workers environment.
Claims (1)
1. the molten iron spheroidising is with the real core spun yarn manufacturing approach of high magnesium alloy metal in the spheroidal graphite cast-iron production process, and with coarse grain magnesium powder or crystallization magnesium grain, coarse granule calcium grain or crystalline calcium grain, magnesium-rare earth alloy powder, industrial silica fume raw material, its each component content is: magnesium 55%; Calcium 10%, rare earth 3%, silicon 32%; With above-mentioned raw materials particle or powder for drying, ball mill mixing, be cold-pressed into diameter and be 130 millimeters powder cylinder biscuit, the biscuit segmentation is heated; Earlier with blank heating to 200 ℃, insulation 1 hour, continue to be warmed up to 500-600 ℃ and be incubated 2 hours again, make it homogenising; Being hot extruded into diameter then is the composite wire of 12mm, will push silk in 300 ℃ of insulations annealing in 1.5 hours, and coming out of the stove is cooled to 50-100 ℃; It is soaked the phytic acid aqueous solution 5 minutes of 1% concentration into; Take out natural air drying then, the stretch percentage elongation of the extruding silk after the annealing surpasses 3%, and the cold-rolled strip with 0.3 millimeter or 0.4 millimeters thick is overmolding to real core metal core-spun yarn on bag core machine at last.
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| CN106086302A (en) * | 2016-07-28 | 2016-11-09 | 上海大学 | Magnesium calcium rare earth alloy core-spun yarn of Ferrous Metallurgy and preparation method thereof |
| CN106086303A (en) * | 2016-07-28 | 2016-11-09 | 上海大学 | Magnesium calcium alloy core-spun yarn of Ferrous Metallurgy and preparation method thereof |
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