CN106702085A - Solid calcium metal, ferrosilicon and titanium-silicon nitride alloy powder composite core spun yarn - Google Patents
Solid calcium metal, ferrosilicon and titanium-silicon nitride alloy powder composite core spun yarn Download PDFInfo
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- CN106702085A CN106702085A CN201611017049.3A CN201611017049A CN106702085A CN 106702085 A CN106702085 A CN 106702085A CN 201611017049 A CN201611017049 A CN 201611017049A CN 106702085 A CN106702085 A CN 106702085A
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- silicon nitride
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
- C21C7/0645—Agents used for dephosphorising or desulfurising
Abstract
The invention relates to alloy core spun yarn, in particular to solid calcium metal, ferrosilicon and titanium-silicon nitride alloy powder composite core spun yarn. The solid calcium metal, ferrosilicon and titanium-silicon nitride alloy powder composite core spun yarn comprises a core layer and a sheet steel layer wrapping the outside of the core layer; a netlike supporting layer made of steel or iron is arranged between the core layer and the sheet steel layer; the core layer comprises a ferrosilicon and titanium-silicon nitride alloy powder layer, a middle protection layer and a solid calcium metal line; the solid calcium metal line is wrapped with the middle protection layer; the ferrosilicon and titanium-silicon nitride alloy powder layer wraps the middle protection layer and is composed of ferrosilicon powder and titanium-silicon nitride alloy powder of which the particle sizes are 3 mm or smaller; and the mass ratio of the solid calcium metal line to the ferrosilicon power to the titanium-silicon nitride alloy powder is 1:(1-2):(2-5). Compared with common solid calcium metal lines, the solid calcium metal, ferrosilicon and titanium-silicon nitride alloy powder composite core spun yarn has the advantages that the yield is higher, the preservation time is longer, the yield is more stable, and remarkable economic benefits are achieved.
Description
Technical field
The present invention relates to a kind of alloy claded wire.
Background technology
China is big steel country, but ratio shared by the quantity and kind of high-quality steel is smaller, can not only meet China's warp
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 above mentioned problem 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 steel
Produce the important symbol converted to modern production.After the nineties in 20th century, the main 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
It is 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 the various additives (deoxidier, desulfurizing agent, alterant, alloy etc.) in molten steel or iron liquid
Certain granularity is broken into, is then included being 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 making steel, molten steel castability is improved, improves the performance of steel, and can significantly carried
Low alloy-consumption, drops in the recovery rate of high alloy, reduces steel-making cost, remarkable in economical benefits.
Titanium silicon nitride core-spun yarn is new composite core-spun yarn in screw-thread steel wire production.Added from the later stage is refined, 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 in Argon station feeds steel by the form of core-spun yarn
Speed enters molten steel, it is to avoid alloy is aoxidized in molten steel by slag；It is on the other hand, low by the molten steel oxidation of deoxidation treatment 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.
Calcium treatment is the required technique of current special steel smelting, and molten steel Calcium treatment is will with injection metallurgical method or injection feeding technology
Calcium metal or alloy add molten steel deep, reach deoxidation, desulfurization, make the outer concise skill of stove of the metallurgical effects such as nonmetal inclusion denaturation
Art.Because the fusing point of calcium metal is low（838℃）, boiling point is also low（1450℃）, the solubility very little in molten steel（When 1600 DEG C,
It is 0.03% when calcium vapour pressure is 0.186MPa）, the density of calcium also very little（1.55g/cm3）, steel is easily floated in addition molten steel
On slag surface with air in oxygen and in slag liquid oxide reaction and scaling loss is fallen.Therefore generally use the core-spun yarn containing calcium metal such as
CaSi core-spun yarns（Ca28%~32%）Or cafe core-spun yarns（Ca about 30%, Fe about 70%）, and treatment when will as far as possible be added to molten metal
Deep, using the static pressure of molten metal, makes calcium being reacted with oxygen, the sulphur etc. in steel before becoming calcium bubble, be unlikely to one plus
Enter to reform into calcium bubble floating to lose.Even so, the recovery rate of calcium metal still only 7~18% or so, substantial amounts of metal
Calcium all unnecessary wastes.Found by substantial amounts of research, by pulvis（Silicon calcium powder or calcium metal, iron powder）The core-spun yarn of composition enters
Softened in the presence of high temperature after ladle, even if wire-feeding velocity higher, core-spun yarn cannot also penetrate high-temperature molten steel entrance
Deep, mostly positioned at the top of molten steel, it is easy to which scaling loss is fallen to slag surface to form calcium bubble floating.
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 the mesh-supported layer that steel or iron are made 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 form 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 non-hardened and tempered steel cost.
The content of the invention
It is an object of the invention to provide a kind of solid calcium metal, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn, by adopting
Alloy and calcium are added in micro alloyed steel with the method for core-spun yarn can not only solve the problems, such as that the rate of recovery is low, while than normal
The solid metal calcium line recovery rate of rule is higher, and the holding time is longer, the more stable advantage of recovery rate, with significant economic effect
Benefit.
In order to realize above-mentioned purpose, present invention employs following technical scheme：
A kind of solid calcium metal, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn, the core-spun yarn include sandwich layer and are wrapped in described
Sheetmetal layer outside sandwich layer, is provided with the mesh-supported layer that steel or iron are made between sandwich layer and sheetmetal layer, the sandwich layer includes ferrosilicon
Titanium silicon nitride alloyed powder last layer, intermediate protective layer and real core metal calcium line, real core metal calcium line are wrapped up by intermediate protective layer, ferrosilicon
Titanium silicon nitride alloyed powder last layer wraps up intermediate protective layer, and described ferrosilicon titanium silicon nitride alloyed powder last layer is that particle diameter is below 3mm
Silicon iron powder and titanium silicon nitride alloy powder, real core metal calcium line and ferrosilicon, the mass ratio of titanium silicon nitride alloy powder are 1:1
~2：2~5；Described titanium silicon nitride alloy powder is made up of following elemental constituent by mass percentage：
Al 1.0~2.5%
N 10~25%
Mn 2.5~5.0%
Mg 1.0~2.5%
Ti 25~40%
P ≤0.1%
S ≤0.1%
Si 25~35%；
Fe surpluses.
Preferably, titanium silicon nitride alloy powder is made up of following elemental constituent by mass percentage：
Al 1.5~2.0%
N 15~20%
Mn 3.0~4.0%
Mg 1.5~2.0%
Ti 30~35%
P ≤0.1%
S ≤0.1%
Si 30~35%；
Fe surpluses.
It is 0.1 ~ 2.0mm as the granularity of preferred titanium silicon nitride alloy powder.
The present invention chooses sponge iron and titanium sponge and ferrosilicon and ferromanganese is smelted in a vacuum furnace.In certain process conditions
Under, nitrogenized, nitridation is reached optimum efficiency（Regulation content）, then pour into ingot casting.Ingot casting is pure into certain particle size through breaking,
A diameter of 13 millimeters of core-spun yarn is overmolding to using iron sheet.This kind of core-spun yarn is inserted into steel in the refining later stage with certain payingoff speed
In liquid, Ti contents averagely reach the recovery rate average 60% of average 55%, the Si of the rate of recovery of 0.008%, Ti in final steel.
Using intermediate protective layer（Box hat）, nexine reality core metal calcium line special construction so that the elevated temperature strength of core-spun yarn
Greatly improve, greatly improve the penetration capacity of core-spun yarn so that calcium metal can veritably be added to molten steel deep, using steel
Hydrostatic, makes calcium metal reacted with oxygen, sulphur etc. in steel before becoming bubble, greatly improves calcium metal recovery rate；It is golden in addition
The specific surface area for belonging to calcium is substantially reduced, therefore reduces the gasification rate of calcium metal, increased calcium metal by molten steel absorb when
Between, thus the rate of recovery and stabilization higher can be obtained in molten steel.
It is compound bag new during steel is produced using solid calcium metal, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn
Heart yearn, adds from the later stage is refined, and can improve the recovery rate of nitrogen in steel titanium silicon, other ferroalloy consumptions is reduced, with significant
Economic benefit.Its reason is that carbon or nitrogen in Ti and steel form size for nano level compound, and they have grown up to crystal grain
Strong inhibition, and volume fraction shared by this nano level compound is when being 2%, to the thinning effect organized most
It is good.
Alloyed powder of the present invention is added in micro alloyed steel by the method using core-spun yarn, with it is following the characteristics of：
1) austenite crystal grows up when preventing soaking：The micro alloyed steels such as Ti are heated during with soaking before forging or rolling, not molten
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 possesses less austenite crystal before power processing, for further fining ferrite grains provide favourable condition.
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 recrystallization and recrystallization, 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 of effective prevention 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
It is made 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 play a decisive role to ferrite grain size,
Precipitation particles is smaller, and volume fraction is bigger, and the ferrite crystal grain for being obtained is also just smaller.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 changing Ti after nitrogen pick-up in alternate distribution, promotes Ti (C, N
) separate out, the particle size of precipitated phase is obviously reduced, so as to enhance the precipitation enhancement of titanium, increase 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,
Ensure under certain strength level, the addition of vanadium can be saved, further reduce the cost of non-hardened and tempered steel.
Specific embodiment
Embodiment 1
A kind of solid calcium metal, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn, the core-spun yarn include sandwich layer and are wrapped in described
Sheetmetal layer outside sandwich layer, is provided with the mesh-supported layer that steel or iron are made between sandwich layer and sheetmetal layer, the sandwich layer includes ferrosilicon
Titanium silicon nitride alloyed powder last layer, intermediate protective layer and real core metal calcium line, real core metal calcium line are wrapped up by intermediate protective layer, ferrosilicon
Titanium silicon nitride alloyed powder last layer wraps up intermediate protective layer, and described ferrosilicon titanium silicon nitride alloyed powder last layer is that particle diameter is below 3mm
Silicon iron powder and titanium silicon nitride alloy powder, real core metal calcium line and ferrosilicon, the mass ratio of titanium silicon nitride alloy powder are 1:
2：3；Described titanium silicon nitride alloy powder is made up of following elemental constituent by mass percentage：
Al 2.0%
N 20%
Mn 4.0%
Mg 2.0%
Ti 30%
P ≤0.1%
S ≤0.1%
Si 35%；
Fe surpluses.
This kind of core-spun yarn is inserted into molten steel in the refining later stage with certain payingoff speed, and Ti contents averagely reach in final steel
The recovery rate average 60% of average 55%, the Si of the rate of recovery of 0.008%, Ti, the recovery rate of Ca is more stable after line feeding, averagely receives
Rate is 30%, average desulfurization degree 26%, highest desulfurization degree 33%, minimum sulfur content 0.006%, and average DNA vaccine 20% is minimum
Oxygen content 0.00082%, pouring molten steel is normal after line feeding, and slab quality is good, shows solid calcium metal cored wire of the present invention also
Can promote inclusion modification, purification molten steel and improve pouring molten steel performance, and can eliminate tundish and casting process
Nozzle clogging phenomenon.And there was only a small amount of splash and Calcium treatment flue dust during line feeding, disclosure satisfy that current steel mill
The advantage of environmentally friendly steel-making requirements.
Embodiment 2
A kind of solid calcium metal, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn, the core-spun yarn include sandwich layer and are wrapped in described
Sheetmetal layer outside sandwich layer, is provided with the mesh-supported layer that steel or iron are made between sandwich layer and sheetmetal layer, the sandwich layer includes ferrosilicon
Titanium silicon nitride alloyed powder last layer, intermediate protective layer and real core metal calcium line, real core metal calcium line are wrapped up by intermediate protective layer, ferrosilicon
Titanium silicon nitride alloyed powder last layer wraps up intermediate protective layer, and described ferrosilicon titanium silicon nitride alloyed powder last layer is that particle diameter is below 3mm
Silicon iron powder and titanium silicon nitride alloy powder, real core metal calcium line and ferrosilicon, the mass ratio of titanium silicon nitride alloy powder are 1:
2：3；Described titanium silicon nitride alloy powder is made up of following elemental constituent by mass percentage：
Al 1.0%
N 15%
Mn 4.0%
Mg 1.0%
Ti 28%
P ≤0.1%
S ≤0.1%
Si 25%；
Fe surpluses.
This kind of core-spun yarn is inserted into molten steel in the refining later stage with certain payingoff speed, and Ti contents averagely reach in final steel
The recovery rate average 60% of average 55%, the Si of the rate of recovery of 0.008%, Ti, the recovery rate of Ca is more stable after line feeding, averagely receives
Rate is 30%, average desulfurization degree 26%, highest desulfurization degree 33%, minimum sulfur content 0.006%, and average DNA vaccine 20% is minimum
Oxygen content 0.00082%, pouring molten steel is normal after line feeding, and slab quality is good, shows solid calcium metal cored wire of the present invention also
Can promote inclusion modification, purification molten steel and improve pouring molten steel performance, and can eliminate tundish and casting process
Nozzle clogging phenomenon.And there was only a small amount of splash and Calcium treatment flue dust during line feeding, disclosure satisfy that current steel mill
The advantage of environmentally friendly steel-making requirements.
Embodiment 3
A kind of solid calcium metal, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn, the core-spun yarn include sandwich layer and are wrapped in described
Sheetmetal layer outside sandwich layer, is provided with the mesh-supported layer that steel or iron are made between sandwich layer and sheetmetal layer, the sandwich layer includes ferrosilicon
Titanium silicon nitride alloyed powder last layer, intermediate protective layer and real core metal calcium line, real core metal calcium line are wrapped up by intermediate protective layer, ferrosilicon
Titanium silicon nitride alloyed powder last layer wraps up intermediate protective layer, and described ferrosilicon titanium silicon nitride alloyed powder last layer is that particle diameter is below 3mm
Silicon iron powder and titanium silicon nitride alloy powder, real core metal calcium line and ferrosilicon, the mass ratio of titanium silicon nitride alloy powder are 1:
2：3；Described titanium silicon nitride alloy powder is made up of following elemental constituent by mass percentage：
Al 2.5%
N 25%
Mn 2.5%
Mg 2.0%
Ti 30%
P ≤0.1%
S ≤0.1%
Si 30%；
Fe surpluses.
This kind of core-spun yarn is inserted into molten steel in the refining later stage with certain payingoff speed, and Ti contents averagely reach in final steel
The recovery rate average 60% of average 55%, the Si of the rate of recovery of 0.008%, Ti, the recovery rate of Ca is more stable after line feeding, averagely receives
Rate is 30%, average desulfurization degree 26%, highest desulfurization degree 33%, minimum sulfur content 0.006%, and average DNA vaccine 20% is minimum
Oxygen content 0.00082%, pouring molten steel is normal after line feeding, and slab quality is good, shows solid calcium metal cored wire of the present invention also
Can promote inclusion modification, purification molten steel and improve pouring molten steel performance, and can eliminate tundish and casting process
Nozzle clogging phenomenon.And there was only a small amount of splash and Calcium treatment flue dust during line feeding, disclosure satisfy that current steel mill
The advantage of environmentally friendly steel-making requirements.
Claims (3)
1. a kind of solid calcium metal, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn, it is characterised in that the core-spun yarn includes sandwich layer
With the sheetmetal layer being wrapped in outside the sandwich layer, the mesh-supported layer that steel or iron are made is provided between sandwich layer and sheetmetal layer, it is described
Sandwich layer includes ferrosilicon titanium silicon nitride alloyed powder last layer, intermediate protective layer and real core metal calcium line, and real core metal calcium line is protected by centre
Sheath is wrapped up, ferrosilicon titanium silicon nitride alloyed powder last layer parcel intermediate protective layer, and described ferrosilicon titanium silicon nitride alloyed powder last layer is
Particle diameter is the silicon iron powder and titanium silicon nitride alloy powder of below 3mm, real core metal calcium line and ferrosilicon, titanium silicon nitride alloy powder
The mass ratio of layer is 1:1~2：2~5；
Described titanium silicon nitride alloy powder is made up of following elemental constituent by mass percentage：
Al 1.0~2.5%
N 10~25%
Mn 2.5~5.0%
Mg 1.0~2.5%
Ti 25~40%
P ≤0.1%
S ≤0.1%
Si 25~35%；
Fe surpluses.
2. a kind of solid calcium metal according to claim 1, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn, its feature
It is that titanium silicon nitride alloy powder is made up of following elemental constituent by mass percentage：
Al 1.5~2.0%
N 15~20%
Mn 3.0~4.0%
Mg 1.5~2.0%
Ti 30~35%
P ≤0.1%
S ≤0.1%
Si 30~35%；
Fe surpluses.
3. a kind of solid calcium metal according to claim 1 and 2, ferrosilicon, titanium silicon nitride alloyed powder composite core-spun yarn, it is special
Levy be titanium silicon nitride alloy powder granularity be 0.1 ~ 2.0mm.
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| CN201611017049.3A CN106702085A (en) | 2016-11-19 | 2016-11-19 | Solid calcium metal, ferrosilicon and titanium-silicon nitride alloy powder composite core spun yarn |
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Cited By (2)
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| CN107365889A (en) * | 2017-07-31 | 2017-11-21 | 马鞍山华盛冶金科技发展有限公司 | A kind of cleanser core-spun yarn of steel-making and preparation method thereof |
| CN112334588A (en) * | 2018-04-03 | 2021-02-05 | 埃尔凯姆公司 | Silicon-based alloy, method for the production thereof and use of such an alloy |
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Application publication date: 20170524 |