CN107312907A - In a kind of control in low-sulfur low-oxygen steel manganese sulfide form method - Google Patents
In a kind of control in low-sulfur low-oxygen steel manganese sulfide form method Download PDFInfo
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- CN107312907A CN107312907A CN201710415390.2A CN201710415390A CN107312907A CN 107312907 A CN107312907 A CN 107312907A CN 201710415390 A CN201710415390 A CN 201710415390A CN 107312907 A CN107312907 A CN 107312907A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
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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
- C21C7/0006—Adding metallic additives
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Abstract
The invention discloses the method for manganese sulfide form in low-sulfur low-oxygen steel in a kind of control；Molten steel can be carried out calcium and magnesium Combined Processing to control the form of MnS in steel in the case where original production technology is constant, after aluminium deoxidation.This method can give full play to the advantage in each comfortable sulfide degenerative process of Ca, Mg alloying element.By being added in steel（By percentage to the quality）0.001~0.02% Mg and 0.001~0.02% Ca, makes sulfide in steel be separated out by core forming core of Mg Al O oxides, reduces sulfide and separates out quantity in crystal boundary.It is simultaneously the complex sulfide containing Ca, Mg alloying element by MnS denaturation, increases substantially the high temperature stability of sulfide, effectively lower sulfide deformation extent in the operation of rolling, the cutting ability of steel is not reduced while the transverse impact toughness for improving steel.
Description
Technical field
The present invention relates to the method for manganese sulfide form in low-sulfur low-oxygen steel in a kind of control.
Background technology
In order to improve the cutting ability of steel, S elements, i.e. resulfurizing series free cutting steel are added generally in steel.Resulfurizing series free cutting steel
Be that yield is maximum in automatic steel, purposes most wide one kind, account for more than the 90% of whole automatic steel yield, be widely used to
Auto parts and components, household electrical appliance, the field such as precision instrument, instrument.Compared with ordinary steel, with the product that it is processed, any surface finish
Spend, tool wear is small, long lifespan, energy consumption is low.According to statistics, machining cost accounts for the ratio of part manufacturing cost up to 40%
~60%.Therefore, improve and improve the cutting ability of steel, the energy consumption of product cost and process can be greatly reduced.
Resulfurizing series free cutting steel can be divided into low-sulfur steel, middle sulphur steel and high-sulfur steel by sulfur content difference in steel.S≤0.025% in steel
For low-sulfur steel, S=0.1~0.3% is high-sulfur steel, and other is middle sulphur steel.Mn/S controls are more than 25 in general low-sulfur steel, high-sulfur steel
Mn/S is controlled between 3~5.Sulfide is main in resulfurizing series free cutting steel exists in MnS forms, in cutting process, MnS
Chip breaking and lubrication are played, so as to improve the cutting ability of steel, tool wear is reduced.However, in the operation of rolling, MnS meetings
Along rolling direction stretcher strain, the MnS after deformation can seriously damage the transverse impact toughness of steel, make material mechanical performance in it is each to
The opposite sex.In order to ensure the cutting ability and isotropism of steel simultaneously, it is sulphur system Cutting free that rationally control is carried out to oxide morphology
The key core problem of steel production field.
It can be divided into three classes according to forms of the MnS in steel as cast condition and distribution：In steel during [O] ＞ 0.02% be I class MnS, in ball
Shape, dispersed distribution；In steel during [O] ＜ 0.01% be II class MnS, in dendritic crystalline, be distributed along crystal boundary；When [O] content is further reduced
For III class MnS, in bulk, it is randomly distributed.I class MnS is smaller to the Effect on Mechanical Properties of steel, and II class and III class MnS are to steel
Effect on Mechanical Properties is larger（Mainly reduce transverse impact toughness）.In order to obtain high degree of purity, so as to ensure high fatigue
[O] is all very low in performance, usual steel, therefore MnS is mainly II class and III class in low-oxygen steel.Therefore in order to eliminate or reduce low-oxygen steel
Adverse effects of the middle MnS to mechanical property, it is therefore necessary to which denaturation treatment is carried out to MnS in steel.
The content of the invention
The present invention is intended to provide in a kind of control in low-sulfur low-oxygen steel manganese sulfide form method.By adding one in steel
Mg, Ca alloying element of fixed number amount, make sulfide in steel be analysed by core forming core of Mg-Al-O or Mg-Ca-Al-O oxides
Go out；MnS denaturation is Mg-Mn-S or Ca-Mn-S or Ca-Mg-Mn-S complex sulfides in steel simultaneously；Improve the height of sulfide
Warm non-deformability, the transverse impact toughness of steel is improved while the cutting ability of steel is ensured.
The present invention is achieved through the following technical solutions：
In a kind of control in low-sulfur low-oxygen steel manganese sulfide form method, comprise the following steps, regulation molten steel in dissolved oxygen quality
Percentage is less than 0.001%；Then add the mass percent of magnesium in magnesium elements, calcium constituent, regulation molten steel for 0.001~
0.02%, the mass percent for adjusting calcium in molten steel is 0.001~0.02%；Last anaerobic cast, in completion in low-sulfur low-oxygen steel
The control of manganese sulfide form.
The invention also discloses a kind of preparation method of the controllable middle low-sulfur low-oxygen steel potting syrup of manganese sulfide form, including
Dissolved oxygen mass percent is less than 0.001% in following steps, regulation molten steel；Then magnesium elements, calcium constituent are added, molten steel is adjusted
The mass percent of middle magnesium is 0.001~0.02%, and the mass percent of calcium is 0.001~0.02% in regulation molten steel；Obtain sulphur
Change the controllable middle low-sulfur low-oxygen steel potting syrup of manganese form.
The invention also discloses a kind of controllable middle low-sulfur low-oxygen steel potting syrup of manganese sulfide form, the manganese sulfide form
The preparation method of controllable middle low-sulfur low-oxygen steel potting syrup comprises the following steps, and dissolved oxygen mass percent is small in regulation molten steel
In 0.001%；Then the mass percent for adding magnesium in magnesium elements, calcium constituent, regulation molten steel is 0.001~0.02%, adjusts steel
The mass percent of calcium is 0.001~0.02% in liquid；Obtain the controllable middle low-sulfur low-oxygen steel potting syrup of manganese sulfide form.
The invention also discloses a kind of preparation method of manganese sulfide form low-sulfur hypoxemia steel ingot in controllable, including following step
Suddenly, dissolved oxygen mass percent is less than 0.001% in regulation molten steel；Then magnesium in magnesium elements, calcium constituent, regulation molten steel is added
Mass percent is 0.001~0.02%, and the mass percent of calcium is 0.001~0.02% in regulation molten steel；Last anaerobic cast,
Cooling and solidifying prepares the controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form.
The invention also discloses a kind of controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form, the manganese sulfide form can control
The preparation method of middle low-sulfur hypoxemia steel ingot comprises the following steps, and dissolved oxygen mass percent is less than 0.001% in regulation molten steel；So
The mass percent for adding magnesium in magnesium elements, calcium constituent, regulation molten steel afterwards is 0.001~0.02%, the quality of calcium in regulation molten steel
Percentage is 0.001~0.02%；Last anaerobic cast, cooling and solidifying prepares the controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form.
The invention also discloses a kind of controllable middle low-sulfur hypoxemia steel part of manganese sulfide form, the manganese sulfide form is controllable
The preparation method of middle low-sulfur hypoxemia steel part comprise the following steps, dissolved oxygen mass percent is less than in regulation molten steel
0.001%；Then the mass percent for adding magnesium in magnesium elements, calcium constituent, regulation molten steel is 0.001~0.02%, adjusts molten steel
The mass percent of middle calcium is 0.001~0.02%；Then anaerobic is poured into a mould, and cooling and solidifying prepares low during manganese sulfide form can control
Sulphur hypoxemia steel ingot；The controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form is finally prepared as the controllable middle low-sulfur of manganese sulfide form low
Oxygen steel part.
The invention also discloses a kind of preparation method of the controllable middle low-sulfur hypoxemia steel part of manganese sulfide form, including it is following
Dissolved oxygen mass percent is less than 0.001% in step, regulation molten steel；Then magnesium in magnesium elements, calcium constituent, regulation molten steel is added
Mass percent be 0.001~0.02%, regulation molten steel in calcium mass percent be 0.001~0.02%；Then anaerobic is poured
Note, cooling and solidifying prepares the controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form；It is finally that the controllable middle low-sulfur of manganese sulfide form is low
Oxygen steel ingot is prepared as the controllable middle low-sulfur hypoxemia steel part of manganese sulfide form, such as can be by preparing steel plate.
In above-mentioned technical proposal, magnesium elements, calcium constituent are added or sequentially added simultaneously；Steel is adjusted using aluminium deoxidation mode
Dissolved oxygen mass percent in liquid.
In above-mentioned technical proposal, magnesium elements come from magnesium or magnesium alloy；Calcium constituent comes from calcium or calcium alloy.
In above-mentioned technical proposal, in molten steel, the mass percent of sulphur is 0.002~0.05%.
The present invention first carries out magnesium processing, then carries out Calcium treatment；Or directly carry out calcium and magnesium processing, i.e., added simultaneously into steel
Calcium and magnesium or calcium-magnesium alloy, it is 0.001~0.02% to make Mg and Ca mass percentage contents in steel.
The present invention carries out Ca, Mg Combined Processing to molten steel, gives full play to association of Ca, Mg element in sulfide degenerative process
Effect advantage：Mg makes steel inclusion become more thin small and scattered, can be separated out for the forming core of sulfide and provide forming core core；Ca
It is easier to be solid-solution in manganese sulfide, improves the high temperature stability of sulfide；Finally exist especially by Ca, Mg Combined Processing
Form that disperse, particle diameter be suitable, the complex sulfide containing hard core, the machinability of low-sulfur low-oxygen steel in improving with this in steel
Energy and anisotropy, improve its comprehensive mechanical property.Prior art carries out denaturation treatment using single-element to manganese sulfide in steel,
Because solubility of the single-element in steel is very low, denaturation treatment is individually carried out to sulfide in steel using a kind of element, usually
Cause inclusion modification not thorough, or cause nozzle blocking.It is of the invention effectively to solve prior art problem.
Such as, in a kind of control in low-sulfur low-oxygen steel manganese sulfide form method, technical points include：
（1）Molten steel carries out deoxidation with Al, controls oxygen content in steel；
（2）Dissolved oxygen content ＜ 0.001% in magnesium processing or calcium and magnesium before processing control steel；
（3）Molten steel after Al deoxidations, allow deoxidation products float 5 minutes after carry out magnesium processing again, i.e., into steel addition Mg or
Mg alloys；Then Calcium treatment is carried out again, i.e., Ca or Ca alloys are added into steel；Or molten steel passes through Al deoxidations, allows deoxidation to produce
After thing floats 5 minutes, calcium and magnesium processing is carried out simultaneously to molten steel, i.e., adds calcium and magnesium or calcium-magnesium alloy simultaneously into steel；
（4）After Calcium treatment, or carry out simultaneously after calcium and magnesium processing, protective casting is carried out under anaerobic, prevents molten steel secondary
Oxidation.
The beneficial effects are mainly as follows：
（1）Ca, Mg Combined Processing reduce respective addition, compared to such as individually being handled using Calcium treatment or magnesium, will not increase steel
Production cost.
（2）The method of the invention need to only add two kinds of alloying elements of Ca, Mg in steel, using adding in original production process
The method of adduction gold, will not change original production technology or original production technology it goes without doing larger change.
（3）The method of the invention can be such that Ca is solid-solution in MnS to form composite sulfuration compared with traditional treatment method, not only
Thing, while Mg, which handles formed oxide, to provide forming core core for the precipitation of sulfide, makes complex sulfide have hard
Core, can further improve its high temperature stability.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the steel inclusion of embodiment 1；
Fig. 2 is 1 point in Fig. 1 of energy spectrum diagram；
Fig. 3 is 2 points in Fig. 1 of energy spectrum diagram；
Fig. 4 is the scanning electron microscope (SEM) photograph of complex sulfide of the embodiment 1 after rolling containing oxide core in steel；
Fig. 5 is the scanning electron microscope (SEM) photograph of the sulfide in steel after rolling of comparative example 1.
Embodiment
In a kind of control in low-sulfur low-oxygen steel manganese sulfide form method, including：
（1）Molten steel carries out deoxidation with Al, controls oxygen content in steel；
（2）Dissolved oxygen content ＜ 0.001% in magnesium processing or calcium and magnesium before processing control steel；
（3）Molten steel after Al deoxidations, allow deoxidation products float 5 minutes after carry out magnesium processing again, i.e., into steel addition Mg or
Mg alloys；Then Calcium treatment is carried out again, i.e., Ca or Ca alloys are added into steel；Or molten steel passes through Al deoxidations, allows deoxidation to produce
After thing floats 5 minutes, calcium and magnesium processing is carried out simultaneously to molten steel, i.e., adds calcium and magnesium or calcium-magnesium alloy simultaneously into steel；
（4）After Calcium treatment, or carry out simultaneously after calcium and magnesium processing, obtain the controllable middle low-sulfur low-oxygen steel cast of manganese sulfide form
Liquid, then carries out protective casting under anaerobic, prevents molten steel secondary oxidation.
According to the above method, 9 stove low-sulfur steels have been smelted in 30kg vaccum sensitive stoves；Wherein 1 stove steel without magnesium, calcium at
Reason, 1 stove steel carries out Calcium treatment, and 1 stove steel carries out magnesium processing；Other 6 stoves are handled by magnesium processing and Calcium treatment or calcium and magnesium.Smelt
Technical process is as follows：About 30kg ingot irons are placed in crucible induction furnace first, induction furnace are then evacuated to 10Pa, so
After be filled with argon gas to 1atm, 10Pa is then evacuated to again, argon gas is then re-filled with to 1atm.It is then electrified to be warming up to 1600
DEG C, it is incubated 5min after molten steel is melting down；Then the feeding chamber above vacuum chamber sequentially adds Mn-Fe, S powder, aluminium block；Insulation
After 5min, embodiment 1 adds magnesium calcium alloy with embodiment 2（Addition is counted according to the recovery rate of Mg, Ca alloying element 10%
Calculate）；Embodiment 3 adds Ni-Mg alloys simultaneously with embodiment 4（Containing Ni80%）With pure calcium line（Wherein Ni-Mg alloys and pure calcium line
Addition calculated according to the recovery rate of Mg, Ca alloying element 10%）；Embodiment 5 adds Ni-Mg alloys with embodiment 6
（Containing Ni80%）, pure calcium line is added after 1min, and wherein the addition of Ni-Mg alloys and pure calcium line is according to Mg, Ca alloying element 10%
Recovery rate calculated；Insulation 5min after under vacuo pour into a mould, cool and solidify be prepared into manganese sulfide form it is controllable in it is low
Sulphur hypoxemia steel ingot；Then 550mm hot rollings test unit on be rolled into thickness be 15mm manganese sulfide form it is controllable in it is low
Sulphur hypoxemia steel plate.Comparative example according to design by this operation, table 1 for experiment steel 6 hotplate body embodiments and 3 stove compared steels it is main
Chemical composition.
Sampled on steel plate, its vertical and horizontal impact property is determined at room temperature.Impact test is according to standard GB/
T229-1994 is tested using Charpy impact machine tester, and test sample size is 10 × 10 × 55mm, and groove is V-type mouthful；Table 2
To test 6 specific embodiments of steel and the impact property of compared steel.The traverse impact value ratio of embodiment steel it can be seen from table
The traverse impact value of compared steel is high, and laterally and longitudinally the ratio between impact value is larger, and the anisotropy of material is smaller.This mainly by
Carried out in steel after magnesium processing and Calcium treatment, sulfide is mingled with Mg-Al-O oxides and separated out for core forming core in steel, such as Fig. 1
With shown in Fig. 2（Fig. 1 is the steel inclusion of embodiment 1）, and MnS is mingled with the complex sulfide being denatured as Mg-Ca-Al-S（Such as
Shown in Fig. 1 and Fig. 3）, improve the high temperature stability of sulfide in steel, such as Fig. 4.Handled and Calcium treatment without magnesium
The non-deformability of sulfide is very poor in steel, steel, after rolling, and sulfide is along rolling direction stretcher strain（Such as Fig. 5 institutes
Show）, this will seriously damage the transverse impact toughness of steel.
The main chemical compositions of the embodiment of table 1 and comparative example（Mass percent）
Note：Unlisted chemical composition is in table：Si 0.05~0.10%, P≤0.015%, N ﹤ 0.005%.
The impact property of the embodiment of table 2 and comparative example
The steel of different tests scheme is subjected to cutting test in laboratory conditions, and according to International Standard Association（ISO）Standard
Examine cutter life（Reach 0.3mm as cutter life using cutter flank wear amount VB）.Cutting test parameter is：Relief angle is
6 °, the depth of cut is 1mm, and the depth of cut is 0.2mm/r, cutting speed v=80~300m/min.Table 3 is 6 of experiment steel specific
The cutting ability of embodiment and comparative example.
The cutting ability of the embodiment of table 3 and comparative example
The present invention can also have other embodiment, and all technical schemes using replacement or equivalent transformation form on an equal basis are all fallen within
Within the scope of application claims.
Claims (10)
1. in a kind of control in low-sulfur low-oxygen steel manganese sulfide form method, it is characterised in that comprise the following steps, adjust molten steel
Middle dissolved oxygen mass percent is less than 0.001%；Then magnesium elements, calcium constituent are added, the mass percent for adjusting magnesium in molten steel is
0.001~0.02%, the mass percent for adjusting calcium in molten steel is 0.001~0.02%；Last anaerobic cast, low-sulfur is low in completion
The control of manganese sulfide form in oxygen steel.
2. in controlling according to claim 1 in low-sulfur low-oxygen steel manganese sulfide form method, it is characterised in that magnesium elements,
Calcium constituent is added or asynchronously added simultaneously；Dissolved oxygen mass percent in molten steel is adjusted using aluminium deoxidation mode.
3. in controlling according to claim 1 in low-sulfur low-oxygen steel manganese sulfide form method, it is characterised in that magnesium elements come
From magnesium or magnesium alloy；Calcium constituent comes from calcium or calcium alloy.
4. in controlling according to claim 1 in low-sulfur low-oxygen steel manganese sulfide form method, it is characterised in that in molten steel,
The mass percent of sulphur is 0.002~0.05%.
5. the controllable middle low-sulfur hypoxemia steel part of a kind of manganese sulfide form, it is characterised in that during the manganese sulfide form is controllable
The preparation method of low-sulfur hypoxemia steel part comprises the following steps, and dissolved oxygen mass percent is less than 0.001% in regulation molten steel；So
The mass percent for adding magnesium in magnesium elements, calcium constituent, regulation molten steel afterwards is 0.001~0.02%, the quality of calcium in regulation molten steel
Percentage is 0.001~0.02%；Then anaerobic is poured into a mould, and cooling and solidifying prepares the controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form；
The controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form is finally prepared as the controllable middle low-sulfur hypoxemia steel part of manganese sulfide form.
6. a kind of preparation method of the controllable middle low-sulfur low-oxygen steel potting syrup of manganese sulfide form, it is characterised in that including following
Dissolved oxygen mass percent is less than 0.001% in step, regulation molten steel；Then magnesium in magnesium elements, calcium constituent, regulation molten steel is added
Mass percent be 0.001~0.02%, regulation molten steel in calcium mass percent be 0.001~0.02%；Obtain manganese sulfide
The controllable middle low-sulfur low-oxygen steel potting syrup of form.
7. a kind of controllable middle low-sulfur low-oxygen steel potting syrup of manganese sulfide form, it is characterised in that the manganese sulfide form is controllable
The preparation method of the middle low-sulfur low-oxygen steel potting syrup of system comprises the following steps, and dissolved oxygen mass percent is less than in regulation molten steel
0.001%；Then the mass percent for adding magnesium in magnesium elements, calcium constituent, regulation molten steel is 0.001~0.02%, adjusts molten steel
The mass percent of middle calcium is 0.001~0.02%；Obtain the controllable middle low-sulfur low-oxygen steel potting syrup of manganese sulfide form.
The preparation method of low-sulfur hypoxemia steel ingot during 8. a kind of manganese sulfide form is controllable, it is characterised in that comprise the following steps, is adjusted
Save dissolved oxygen mass percent in molten steel and be less than 0.001%；Then the quality hundred of magnesium in magnesium elements, calcium constituent, regulation molten steel is added
Fraction is 0.001~0.02%, and the mass percent of calcium is 0.001~0.02% in regulation molten steel；Last anaerobic cast, cooling is solid
Change prepares the controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form.
Low-sulfur hypoxemia steel ingot during 9. a kind of manganese sulfide form is controllable, it is characterised in that low during the manganese sulfide form is controllable
The preparation method of sulphur hypoxemia steel ingot comprises the following steps, and dissolved oxygen mass percent is less than 0.001% in regulation molten steel；Then plus
The mass percent for entering magnesium in magnesium elements, calcium constituent, regulation molten steel is 0.001~0.02%, the quality percentage of calcium in regulation molten steel
Number is 0.001~0.02%；Last anaerobic cast, cooling and solidifying prepares the controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form.
10. the preparation method of the controllable middle low-sulfur hypoxemia steel part of a kind of manganese sulfide form, it is characterised in that including following step
Suddenly, dissolved oxygen mass percent is less than 0.001% in regulation molten steel；Then magnesium in magnesium elements, calcium constituent, regulation molten steel is added
Mass percent is 0.001~0.02%, and the mass percent of calcium is 0.001~0.02% in regulation molten steel；Then anaerobic is poured into a mould,
Cooling and solidifying prepares the controllable middle low-sulfur hypoxemia steel ingot of manganese sulfide form；Finally by the controllable middle low-sulfur low-oxygen steel of manganese sulfide form
Ingot is prepared as the controllable middle low-sulfur hypoxemia steel part of manganese sulfide form.
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| CN112210648A (en) * | 2020-10-12 | 2021-01-12 | 马鞍山钢铁股份有限公司 | Process for separating micron-scale pure MnS from low-sulfur steel through temperature control rolling |
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| CN105671434A (en) * | 2016-03-19 | 2016-06-15 | 上海大学 | Magnesium, calcium and sulfur containing 20MnCr free-cutting gear steel and preparation method thereof |
| CN105803308A (en) * | 2016-03-19 | 2016-07-27 | 上海大学 | Magnesium and calcium-containing 45MnVS free machining quenched and tempered steel and manufacturing method thereof |
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| CN112210648A (en) * | 2020-10-12 | 2021-01-12 | 马鞍山钢铁股份有限公司 | Process for separating micron-scale pure MnS from low-sulfur steel through temperature control rolling |
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Application publication date: 20171103 |