CN106636544A - Titanium-silicon nitride alloy cored wire containing rare earth, calcium, barium and molybdenum - Google Patents

Titanium-silicon nitride alloy cored wire containing rare earth, calcium, barium and molybdenum Download PDF

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Publication number
CN106636544A
CN106636544A CN201611015735.7A CN201611015735A CN106636544A CN 106636544 A CN106636544 A CN 106636544A CN 201611015735 A CN201611015735 A CN 201611015735A CN 106636544 A CN106636544 A CN 106636544A
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Prior art keywords
silicon nitride
rare earth
barium
calcium
steel
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Chinese (zh)
Inventor
凌春源
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ZHEJIANG BAOXIN NEW FURNACE TECHNOLOGY DEVELOPMENT Co Ltd
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ZHEJIANG BAOXIN NEW FURNACE TECHNOLOGY DEVELOPMENT Co Ltd
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Priority to CN201611015735.7A priority Critical patent/CN106636544A/en
Publication of CN106636544A publication Critical patent/CN106636544A/en
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • B22F1/0003
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006Adding metallic additives
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04Removing impurities by adding a treating agent
    • C21C7/06Deoxidising, e.g. killing
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/16Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Abstract

The invention relates to an alloy cored wire, in particular to a titanium-silicon nitride alloy cored wire containing rare earth, calcium, barium and molybdenum. The titanium-silicon nitride alloy cored wire containing rare earth, calcium, barium and molybdenum comprises a core layer and a steel skin layer wrapping the core layer. The core layer is titanium-silicon nitride alloy powder which contains rare earth, calcium, barium and molybdenum and has the particle sizes below 3 mm. A netty supporting layer made of steel or iron is arranged between the core layer and the steel skin layer. The titanium-silicon nitride alloy powder containing rare earth, calcium, barium and molybdenum is prepared from, by mass, 1.0%-2.5% of Al, 10%-25% of N, 2.5%-5.0% of Mn, 1.0%-2.5% of Mg, 25%-40% of Ti, 25%-35% of Si, 5%-10% of Ca, 0.5%-1.0% of Mo, 0.5%-1.0% of Ba, 1.0%-2.0% of rare earth elements, no more than 0.1% of P, no more than 0.1% of S, and the balance Fe. The alloy powder is added into microalloyed steel through a cored wire method so that the problem of low recovery rate can be solved, consumption of ferrosilicon and ferromanganese can be reduced, application of titanium-silicon nitride and the titanium-silicon nitride cored wire is developed, and remarkable economic benefits are achieved.

Description

One kind contains rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire
Technical field
The present invention relates to a kind of alloy claded wire.
Background technology
China is big steel country, but the ratio shared by the quantity and kind of high-quality steel is less, can not only meet China Jing Ji builds the requirement with national defense construction, and the waste of resource is quite serious, and the cost for causing smelting iron and steel is continuously increased.Solution Certainly the fundamental way of the problems referred to above is that the novel metallurgical subject-micro-alloying technology occurred using 20 century 70s is existed Micro (0.001%-0.1%) alloying element is added in steel, just can be to the performance of steel (such as high intensity, high tenacity, good solderable Property and corrosion resistance) reach significant improvement, while saving valuable alloying element, with reduces cost, this is traditional iron and steel Produce the important symbol to modern production conversion.After the nineties in 20th century, the main iron and steel producing country of China and the world makes in succession Development plan that is fixed and implementing New Generation Steel PRODUCTION TRAITS, super fine organization, high-cleanness, high, high evenness micro alloyed steel into For the Main Trends of The Development of ferrous materials.At present, micro alloyed steel accounts for the total ratio most of steel, and world average level is about 15%, Industrialized country reaches 30%, and China is less than 5%, therefore China's urgent need micro-alloying technology transforms the original low-alloy of China High-strength steel system, and micro alloyed steel kind and Iron & Steel Material of New Generation that exploitation is badly in need of are combined with controlled rolling and controlled cooling.
Core-spun yarn is to be intended to add molten steel or the various additives (deoxidier, desulfurizing agent, alterant, alloy etc.) in iron liquid Certain granularity is broken into, is then included for a composite with random length with cold-rolled low carbon steel band.Cored Line technology is a kind of external refining means for growing up on the basis of spraying metallurgy technology the eighties.Core-spun yarn is applied to steel-making And casting.Steel inclusion morphology can be purified for steel-making, molten steel castability is improved, improves the performance of steel, and can significantly be carried Low alloy-consumption, drops in heavy alloyed recovery rate, reduces steel-making cost, remarkable in economical benefits.
Titanium silicon nitride core-spun yarn is composite core-spun yarn new in screw-thread steel wire production.Add from the refining later stage, can The recovery rate of nitrogen in steel titanium is improved, other ferroalloy consumptions is reduced, with significant economic benefit.Due to titanium silicon nitride alloy Proportion kicks the beam(Iron content is lower than ferro-titanium by more than 30% in titanium silicon nitride alloy), in adition process, swim in molten steel surface And combined with slag and be oxidized, cause the recovery rate of titanium relatively low(Average out to 27%), Ti content 0.0038% in steel do not reach matter Amount internally controlling requirement.On the one hand can be that alloy is fast and titanium silicon nitride alloy is fed in steel at Argon station by the form of core-spun yarn Speed enters molten steel, it is to avoid alloy is aoxidized in molten steel by slag;On the other hand, the molten steel oxidation of deoxidation treatment is low after stove, The scaling loss of titanium can be reduced, so as to improve and stablize the rate of recovery of the titanium in steel.
The application for a patent for invention of applicant's application(Application number:201510160282.6, applying date 2015.04.07)It is open A kind of titanium silicon nitride core-spun yarn, including sandwich layer and the sheetmetal layer that is wrapped in outside the sandwich layer, the sandwich layer is titanium silicon nitride Alloy-layer, is provided with mesh-supported layer made by steel or iron between the sandwich layer and sheetmetal layer, the titanium silicon nitride alloy-layer is by grain Footpath constitutes for the titanium silicon nitride alloying pellet of below 3mm.Carbon or nitrogen in the Ti of the invention and steel forms size for nano level Compound, they are best to the thinning effect organized, and improve the intensity of ferrous materials, and nitrogen pick-up improves the stability of TiN particles, more Effectively prevent Austenite Grain Growth.Cheap nitrogen is made full use of, in the case where certain strength level is ensured, titanium can be saved Addition, further reduce the cost of non-hardened and tempered steel.
The content of the invention
It is an object of the invention to provide a kind of contain rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire, by adopting cored The method of line to be added to micro alloyed steel in can not only solve the problems, such as that the rate of recovery is low, and ferrosilicon, ferromanganese can also be saved Usage amount, exploitation titanium silicon nitride and its core-spun yarn Alloyapplication, with significant economic benefit.
In order to realize above-mentioned purpose, following technical scheme is present invention employs:
One kind contains rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire, and the core-spun yarn includes sandwich layer and is wrapped in outside the sandwich layer The sheetmetal layer in portion, it is below 3mm containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder, the sandwich layer that the sandwich layer is particle diameter Mesh-supported layer made by steel or iron is provided with and sheetmetal layer between, containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder quality is pressed Percentage is made up of elements below component:
Al 1.0 ~ 2.5%,
N 10 ~ 25%,
Mn 2.5 ~ 5.0%,
Mg 1.0 ~ 2.5%,
Ti 25 ~ 40%,
Si 25 ~ 35%,
Ca 5 ~ 10%,
Mo 0.5 ~ 1.0%,
Ba 0.5 ~ 1.0%,
Rare earth element 1.0 ~ 2.0%,
P≤0.1%,
S ≤0.1%;
Fe surpluses.
Preferably, containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder by mass percentage by elements below component Constitute:
Al 1.5 ~ 2.0%,
N 15 ~ 20%,
Mn 3.0 ~ 4.0%,
Mg 1.5 ~ 2.0%,
Ti 30 ~ 35%,
Si 30 ~ 35%,
Ca 5 ~ 10%,
Mo 0.5 ~ 1.0%,
Ba 0.5 ~ 1.0%,
Rare earth element 1.0 ~ 2.0%,
P ≤0.1%
S ≤0.1%;
Fe surpluses.
Preferably, the granularity containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder is 0.1 ~ 2.0mm.
The present invention chooses each component raw material and smelts in a vacuum furnace.Under certain process conditions, nitrogenized, made nitridation Reach optimum efficiency(Regulation content), then pour into ingot casting.The broken essence of ingot casting Jing is overmolding to diameter into certain particle size using iron sheet For 13 millimeters of core-spun yarn.This kind of core-spun yarn is inserted into molten steel in the refining later stage with certain payingoff speed, and Ti contains in final steel Amount averagely reaches the recovery rate average 60% of average 55%, the Si of the rate of recovery of 0.008%, Ti.
Using the present invention containing rare earth, calcium, barium, the high titanium titanium silicon nitride alloyed powder of molybdenum core-spun yarn be iron and steel production in it is new Composite core-spun yarn, adds from the refining later stage, can improve the recovery rate of nitrogen in steel titanium silicon, reduces other ferroalloy consumptions, has Significant economic benefit.Its reason is that Ti and carbon or nitrogen in steel form size for nano level compound, and they are to crystal grain Grow up strong inhibition, and the volume fraction shared by this nano level compound is when being 2%, the refinement to organizing Effect is best.Ca improves the clarity of the form of field trash and distribution cleaning molten steel, improves the quality of steel, can improve molten steel The quality of mobile performance and steel.Ba is active element, it is possible to decrease inclusion content in melting steel content, increased the flowing of molten steel, makes steel Water is more uniform.Compound use Ca, Ba deoxidation, its product can form polynary mutual solution, reduce the activity and fusing point of deoxidation products. Ba can play a part of to promote Ca, be conducive to deoxidation to carry out, and make molten steel purifying effect more preferably, be conducive to steel inclusion to assemble Float.Compound use Ca, Ba deoxidation, product is the composite oxides of low melting point, is conducive to steel inclusion aggregation to float. And the activity and fusing point of deoxidation products can be reduced, is conducive to deoxidation to carry out, make molten steel purifying effect more preferable.Rare earth element is referred to Period of element atom ordinal number is 15 lanthanide series of 57-71.These elements are all metals, but their oxide much like " soil ", so traditionally claiming rare earth.Rare earth is added in steel, thus it is possible to vary the composition of steel inclusion, form, distribution and property, So as to improve the various performances of steel, such as toughness, weldability, cold-forming property.
Alloyed powder of the present invention by using the method for core-spun yarn to be added to micro alloyed steel in, with it is following the characteristics of:
1) austenite crystal grows up when preventing soaking:The micro alloyed steels such as Ti are not molten in heating before forging or rolling and soaking The migration of the microalloy carbonitride Pinning austenite grain boundary of solution, prevents its crystal grain from growing up, thus makes micro alloyed steel in pressure Just possess less austenite crystal before power processing, for further fining ferrite grains favourable condition is provided.
2) austenite recrystallization is prevented during ausforming:During ausforming, analysed by strain inducing Crystal grain is grown up after the carbonitride precipitates of the Ti for going out can suppress deformed austeaite to recrystallize and recrystallize, and plays crystal grain thinning Effect.Because the carbonitride particle preferential precipitation of the microalloy element of strain induced precipitate is in austenite crystal in hot procedure On boundary, sub boundary and dislocation line, so as to the motion for effectively preventing crystal boundary, sub boundary and dislocation, its effect can not only be prevented The beginning of recrystallization process, and the carrying out of recrystallization process can also be suppressed.
3) precipitation enhancement after ferrite transformation:After ausforming, will there is ferrite transformation, at this moment will there is big The disperse microalloy carbonitride particle of amount is separated out, and these particles for separating out equally also play pinning effect to ferrite crystal grain, limit Make it to grow up.On the other hand, these particles also play precipitation enhancement, improve the intensity of ferrous materials.
4)The size and its volume fraction of microalloy Carbonitride Precipitation particle plays a decisive role to ferrite grain size, Precipitation particles is less, and volume fraction is bigger, and the ferrite crystal grain for being obtained is also less.Thus, effort has precipitation particles Larger volume fraction and less size is the big target in grain refinement process, while being also the direction of invention.Adding While entering these rare elements, while nitrogen pick-up, because Ti is changed after nitrogen pick-up in alternate distribution, promotes Ti (C, N ) separate out, the particle size for making precipitated phase is obviously reduced, and so as to enhance the precipitation enhancement of titanium, increases substantially steel Intensity.Nitrogen is separated out by promoting Ti (C, N), and effectively pinning austenite-ferrite grain boundaries, have refined ferrite brilliant Grain.Nitrogen pick-up may additionally facilitate the formation of Intragranular Acicular Ferrite, further refine ferritic structure.To Trace Titanium Treatment non-hardened and tempered steel, Nitrogen pick-up improves the stability of TiN particles, more effectively prevents Austenite Grain Growth.Cheap nitrogen is made full use of, Under ensureing certain strength level, the addition of vanadium can be saved, further reduce the cost of non-hardened and tempered steel.
Specific embodiment
Embodiment 1
One kind contains rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire, and the core-spun yarn includes sandwich layer and is wrapped in outside the sandwich layer The sheetmetal layer in portion, it is below 3mm containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder, the sandwich layer that the sandwich layer is particle diameter Mesh-supported layer made by steel or iron is provided with and sheetmetal layer between, containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder quality is pressed Percentage is made up of elements below component:
Al 2.0%,
N 20%,
Mn 4.0%,
Mg 2.0%,
Ti 30%,
Si 35%,
Ca 5%,
Mo 1.0%,
Ba 1.0%,
Rare earth element 1.0%,
P≤0.1%,
S ≤0.1%;
Fe surpluses.
The present invention chooses each component raw material and smelts in a vacuum furnace.Under certain process conditions, nitrogenized, made nitridation Reach optimum efficiency(Regulation content), then pour into ingot casting.The broken essence of ingot casting Jing is overmolding to diameter into certain particle size using iron sheet For 13 millimeters of core-spun yarn.This kind of core-spun yarn is inserted into molten steel in the refining later stage with certain payingoff speed, and Ti contains in final steel Amount averagely reaches the recovery rate average 60% of average 55%, the Si of the rate of recovery of 0.008%, Ti.
Embodiment 2
One kind contains rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire, and the core-spun yarn includes sandwich layer and is wrapped in outside the sandwich layer The sheetmetal layer in portion, it is below 3mm containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder, the sandwich layer that the sandwich layer is particle diameter Mesh-supported layer made by steel or iron is provided with and sheetmetal layer between, containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder quality is pressed Percentage is made up of elements below component:
Al 1.0%,
N 15%,
Mn 4.0%,
Mg 1.0%,
Ti 25%,
Si 25%,
Ca 5%,
Mo 1.0%,
Ba 1.0%,
Rare earth element 1.0%,
P≤0.1%,
S ≤0.1%;
Fe surpluses.
The present invention chooses each component raw material and smelts in a vacuum furnace.Under certain process conditions, nitrogenized, made nitridation Reach optimum efficiency(Regulation content), then pour into ingot casting.The broken essence of ingot casting Jing is overmolding to diameter into certain particle size using iron sheet For 13 millimeters of core-spun yarn.This kind of core-spun yarn is inserted into molten steel in the refining later stage with certain payingoff speed, and Ti contains in final steel Amount averagely reaches the recovery rate average 60% of average 55%, the Si of the rate of recovery of 0.008%, Ti.
Embodiment 3
One kind contains rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire, and the core-spun yarn includes sandwich layer and is wrapped in outside the sandwich layer The sheetmetal layer in portion, it is below 3mm containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder, the sandwich layer that the sandwich layer is particle diameter Mesh-supported layer made by steel or iron is provided with and sheetmetal layer between, containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder quality is pressed Percentage is made up of elements below component:
Al 2.5%,
N 25%,
Mn 2.5%,
Mg 2.0%,
Ti 30%,
Si 28%,
Ca 10%,
Mo 1.0%,
Ba 1.0%,
Rare earth element 1.0%,
P≤0.1%,
S ≤0.1%;
Fe surpluses.
The present invention chooses each component raw material and smelts in a vacuum furnace.Under certain process conditions, nitrogenized, made nitridation Reach optimum efficiency(Regulation content), then pour into ingot casting.The broken essence of ingot casting Jing is overmolding to diameter into certain particle size using iron sheet For 13 millimeters of core-spun yarn.This kind of core-spun yarn is inserted into molten steel in the refining later stage with certain payingoff speed, and Ti contains in final steel Amount averagely reaches the recovery rate average 60% of average 55%, the Si of the rate of recovery of 0.008%, Ti.

Claims (3)

1. it is a kind of to contain rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire, it is characterised in that the core-spun yarn includes sandwich layer and parcel Sheetmetal layer outside the sandwich layer, it is below 3mm containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloyed powder that the sandwich layer is particle diameter End, is provided with mesh-supported layer made by steel or iron between the sandwich layer and sheetmetal layer, containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy Powder is made up of by mass percentage elements below component:
Al 1.0 ~ 2.5%,
N 10 ~ 25%,
Mn 2.5 ~ 5.0%,
Mg 1.0 ~ 2.5%,
Ti 25 ~ 40%,
Si 25 ~ 35%,
Ca 5 ~ 10%,
Mo 0.5 ~ 1.0%,
Ba 0.5 ~ 1.0%,
Rare earth element 1.0 ~ 2.0%,
P≤0.1%,
S ≤0.1%;
Fe surpluses.
2. it is according to claim 1 a kind of containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire, it is characterised in that containing dilute Soil, calcium, barium, molybdenum titanium silicon nitride alloy powder are made up of by mass percentage elements below component:
Al 1.5 ~ 2.0%,
N 15 ~ 20%,
Mn 3.0 ~ 4.0%,
Mg 1.5 ~ 2.0%,
Ti 30 ~ 35%,
Si 30 ~ 35%,
Ca 5 ~ 10%,
Mo 0.5 ~ 1.0%,
Ba 0.5 ~ 1.0%,
Rare earth element 1.0 ~ 2.0%,
P ≤0.1%
S ≤0.1%;
Fe surpluses.
3. according to claim 1 and 2 a kind of containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy claded wire, it is characterised in that Granularity containing rare earth, calcium, barium, molybdenum titanium silicon nitride alloy powder is 0.1 ~ 2.0mm.
CN201611015735.7A 2016-11-18 2016-11-18 Titanium-silicon nitride alloy cored wire containing rare earth, calcium, barium and molybdenum Withdrawn CN106636544A (en)

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Application Number Priority Date Filing Date Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111500821A (en) * 2020-05-20 2020-08-07 李素坤 Preparation method of steel for composite cored wire and high heat input welding

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111500821A (en) * 2020-05-20 2020-08-07 李素坤 Preparation method of steel for composite cored wire and high heat input welding
CN111500821B (en) * 2020-05-20 2022-01-18 李素坤 Preparation method of steel for composite cored wire and high heat input welding

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