CN107008872B - Grain refiner for ferritic stainless steel continuous casting and preparation method thereof and application method - Google Patents
Grain refiner for ferritic stainless steel continuous casting and preparation method thereof and application method Download PDFInfo
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- CN107008872B CN107008872B CN201710137152.XA CN201710137152A CN107008872B CN 107008872 B CN107008872 B CN 107008872B CN 201710137152 A CN201710137152 A CN 201710137152A CN 107008872 B CN107008872 B CN 107008872B
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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
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/108—Feeding additives, powders, or the like
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0264—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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Abstract
The invention discloses a kind of grain refiner for ferritic stainless steel continuous casting, raw material composition and weight percent are as follows: TiC powder 0.01~0.05%, pure Fe powder 99.99~99.95%；The density of 1 μm of the partial size < of TiC powder, partial size particle of TiC powder in 10~20 μm, the grain refiner of the pure Fe powder are greater than 20000/mm3.Preparation method includes the following steps: (1) abrasive material: bulky grain TiC made from carbothermic method being placed in planetary mills and is ground, average grain diameter is ground to less than 1 μm, obtains micron-sized TiC powder；(2) it mixes: obtained micron order TiC powder and partial size is weighed in 10~20 μm of pure Fe powder according to raw material weight percentage respectively, be placed in ball mill and be uniformly mixed；(3) hip moulding: the mixed powder obtained after step (2) are mixed carries out hip moulding.In ferritic stainless steel continuous casting, by adding grain refiner of the invention, ferrite stainless steel continuous casting billet column crystal ratio is greatly reduced, and proportion of equiaxed grain is improved to 70% or more, and grain refining effect is significant.
Description
Technical field
The present invention relates to metal material grain refinement technology fields, more particularly relate to a kind of for ferritic stainless steel company
The grain refiner and its preparation and application of casting.
Background technique
Stainless steel refers to the general name for resisting the steel alloys of corrosivenesses such as atmosphere, acid, alkali and salt.Specific to it
Rustless property, corrosion resistance, heat resistance, low-temperature flexibility, bio-neutral, chemical compatibility, dicoration, processing and manufacturing property, service life be long, can
Many advantages, such as recycling, has been widely used in industry, agricultural, the every field of national defence and people's daily life, demand
Amount also increases year by year, and national stainless steel output has reached 22,000,000 tons within 2015.According to alloying element and the difference of microscopic structure
It can be divided into: ferritic stainless steel, austenitic stainless steel, martensitic stain less steel and two phase stainless steel.Wherein ferritic stainless steel is made
To be a kind of using chromium as the steel grade of main alloy element, have containing formability possessed by nickel and stainless steel, economy, corrosion resistance, resists
There is the performances such as oxidisability at low cost, anticorrosion stress-resistant distinguishing features, referred to as economical stainless steel, the application such as to have excellent performance
It has a extensive future.With the development of the social economy, more stringent requirements are proposed for the development of people's stainless steel, in addition to " stainless ", " warp
Ji " outside, also requires it with excellent mechanics and mechanical performance.
Ferritic stainless steel is substantially Fe-Cr or Fe-Cr-Mo alloy, this kind of alloy column crystal ratio in process of setting
It is more developed, it easily causes to be segregated, fold usually occurs in surface during following process, and then influences the surrender and tension of steel
The mechanical properties such as intensity, therefore wish to control the development of column crystal in production, segregation is reduced, the appearance of fold is avoided.Fine grain is strong
Change and be widely used in stainless steel production as a kind of schedule of reinforcement that intensity can be improved simultaneously and do not damage toughness, by thin
Change crystal grain, proportion of equiaxed grain can be improved, reduce or eliminate column crystal, segregation can be effectively reduced, improves the comprehensive mechanical property of steel
Energy.The method of refinement crystal grain mainly has at present: 1, method for quick cooling；2, mechanical-physical refines method；3, microalloying refinement iron element
Body crystal grain；4, fining agent is added.Wherein method for quick cooling is more commonly used when producing simple small articles or pulverulent product, to big
The production of type heavv section casting is difficult to realize, and this method is not easy to operate, and human factor and contingency are larger；Mechanical-physical is thin
Change method is complicated for operation, and consumption is big, easily incorporation impurity, and thinning effect is unstable；Microalloy method to steel structure refinement have compared with
Big limitation will often carry out comprehensive refinement in conjunction with certain heat processing technique, can just obtain preferable effect, thus produce
Higher cost, while increasing carrying capacity of environment；The method of addition fining agent can add during smelting into metal bath
Refinement agent promotes a point homogeneous nucleation, and coarse as-cast structure is made to become tiny equiax crystal, improves proportion of equiaxed grain, realizes
Crystal grain refinement." crystal fining method of steel, the grain refining alloy of steel and the production crystalline substance that Chinese patent CN1396960A is announced
Grain refining alloy method ", Chinese patent announce CN101407866A announce " the Fe-Ti-N grain refiner and its system of steel
Preparation Method ", Chinese patent announce CN101649411A announce " Fe-X-C grain refiner and preparation method thereof ", Chinese patent
" crystal fining method of high temperature steel alloy large forgings " and Chinese patent CN that the CN 102134637A of announcement is announced
" the nuclear reactor evaporator method for refining grains of heavy forging steel " that 102234706A is announced is by adding crystal grain into molten steel
The method of fining agent refines crystal grain, but it is for cast member.It is generally used in present iron and steel enterprise producing stainless steel process
Conticaster is produced, at present there is no the grain refiner and adding method specifically for continuous casting process, the addition crystal grain made
Fining agent method is not applied well on continuous casting billet.
Summary of the invention
The present invention be directed to the prior arts to be directed to grain refiner used in stainless steel continuous casting production technology and addition not yet
The deficiency of method is, and it is an object of the present invention to provide a kind of grain refiner and its side of making and using for ferritic stainless steel continuous casting
Method, to be used for ferritic stainless steel continuous casting process.
To achieve the above object, the present invention provides a kind of grain refiners for ferritic stainless steel continuous casting, former
Material composition and weight percent are as follows: TiC powder 0.01~0.05%, remaining is greater than 99.95% Fe powder for content；The TiC powder
1 μm of partial size <, the partial size of the Fe powder is 10~20 μm, and the grain density of TiC powder is greater than 20000 in the grain refiner
A/mm3。
The present invention also provides the preparation method of the above-mentioned grain refiner for ferritic stainless steel continuous casting, the crystal grain
The preparation method of fining agent includes the following steps:
(1) abrasive material: bulky grain TiC made from carbothermic method is placed in planetary mills and is ground, it is small to be ground to average grain diameter
In 1 μm, micron-sized TiC powder is obtained；
(2) mix: by obtained micron order TiC powder and partial size 10~20 μm Fe powder according to TiC powder and Fe powder weight
Amount percentage is weighed respectively, is placed in ball mill and is uniformly mixed；
(3) hip moulding: the mixed powder obtained after step (2) are mixed carries out hip moulding, is used for
The grain refiner of ferritic stainless steel continuous casting.
Further, in the step (2), incorporation time is 30~50min.
Further, in the step (3), hip moulding temperature is 1200 DEG C~1300 DEG C, and pressure is greater than
15MPa。
The present invention also provides the application method of the above-mentioned grain refiner for ferritic stainless steel continuous casting, users
Method is that the grain refiner is added in molten steel in continuous casting production process tundish station.
The features of the present invention also characterized in that the additive amount of grain refiner is the crystal grain refinement that steel per ton adds 100~500g
Agent, molten steel overheat is 10~15 DEG C when addition, and addition manner is to throw.
Compared with the existing technology, beneficial effects of the present invention are as follows:
The present invention is directed to grain refiner and addition side used in stainless steel continuous casting production technology for the prior art not yet
The status of method provides a kind of grain refiner and its preparation and application for ferritic stainless steel continuous casting, preparation
Grain refiner can be carried out dedicated for ferritic stainless steel continuous casting process using in the use of ferritic stainless steel continuous casting
When, by adding grain refiner of the invention, ferrite stainless steel continuous casting billet column crystal ratio is greatly reduced, proportion of equiaxed grain
It improves to 70% or more, grain refining effect is significant.
Detailed description of the invention
Fig. 1 is the metallographic comparison diagram of the embodiment of the present invention 1, and (a) adds TiC (b) blank.
Fig. 2 is the ferritic stainless steel microstructure of the different content TiC of the embodiment of the present invention 1, (a) 0.01% (b)
0.02% (c) 0.03% (d) 0.05%.
Fig. 3 is the electron-microscope scanning figure of the embodiment of the present invention 3, wherein (a) Al2O3-SiO2- MnO field trash (b) MgO field trash
(c)SiO2Field trash (d) TiC field trash.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Grain refiner provided in an embodiment of the present invention for ferritic stainless steel continuous casting, raw material composition and weight hundred
Divide ratio are as follows: TiC powder 0.01~0.05%, Fe powder 99.99~99.95%, Fe powder are purchased for laboratory；
1 μm of the partial size < of TiC powder, the partial size of Fe powder is at 10~20 μm, and the density of the particle of TiC powder is big in grain refiner
In 20000/mm3。
The preparation method of grain refiner provided in an embodiment of the present invention for ferritic stainless steel continuous casting, specifically includes
Following steps:
(1) abrasive material: bulky grain TiC made from carbothermic method is placed in planetary mills and is ground, it is small to be ground to average grain diameter
In 1 μm, micron-sized TiC powder is obtained；
Carbothermic method: with TiO2It is raw material with carbon black, is added in the tube furnace of argon air-flow protection and adds after high-energy ball milling
Heat keeps the temperature 1h to 1259 DEG C~1500 DEG C.Product obtains the near-stoichiometric TiC powder of grain size about 80nm.
Grinding: the rotational velocity 425r/min of ball mill, Ball-milling Time 25min.
Planetary mills model: QMSB-4 type planetary high-energy ball mill
(2) it mixes: by obtained micron order TiC powder and partial size in 10~20 μm of Fe powder according to raw material weight percentage score
It is not weighed, is placed in ball mill and is uniformly mixed, with the extension of time, the content of small particle powder is gradually increased, still
The trend of increase gradually slows down, it can be observed that when 30min and 50min size distribution experiment difference very little, in fining agent
Meso-position radius reduces with the increase of time, reaches minimum in 30min, as the extension of time no longer reduces；
(3) hip moulding: the mixed powder obtained after step (2) are mixed carries out hip moulding.
In embodiments of the present invention, in step (2), incorporation time is 30~50min.
In embodiments of the present invention, in step (3), hip moulding temperature is 1200 DEG C, pressure 15MPa, heat etc.
The hydrostatic profile time is 30~50min.It can be found that hip temperature is constant preferable mixing effect in this temperature range
Fruit, and with pressure rise, TiC grain density is gradually increased, when pressure is greater than 15MPa, TiC particle in grain refiner
Density is greater than 20000/mm3。
The application method of grain refiner provided in an embodiment of the present invention for ferritic stainless steel continuous casting is, will be made
The standby grain refiner for ferritic stainless steel continuous casting is added in molten steel in continuous casting production process tundish station.
In embodiments of the present invention, the additive amount of grain refiner is steel 100g~500g per ton, and molten steel overheats when addition
Degree is 10~15 DEG C, and addition manner is to throw.
Embodiment 1
Influence of the grain refiner to 430L ferritic stainless steel microstructure
As shown in Figure 1, from metallographic structure it can be found that TiC can be significantly improved in structure of steel as grain refiner
Equiaxed zone ratio, little crystal grain quantity increase, and when TiC content is 0.03%, thinning effect is best, when TiC content continues growing
When, thinning effect does not change substantially.
As can be known from Fig. 2, the quantity of acicular ferrite increases with the increase of TiC content, and size constantly reduces, when
Optimum state is presented in TiC content when reaching 0.03%, acicular ferrite is tiny, intensive, shows the state of segmentation crystal grain, plays
Refine the effect of crystal grain.When TiC additive amount reaches 0.05%, the variation of ferrite pattern and quantity is not obvious, substantially with
It is close when 0.03%.
Embodiment 2
Influence of the grain refiner to 430L ferritic stainless steel grain size
Grain refiner is thrown to molten steel in continuous casting production, additional amount is steel 300g per ton, and comparative example is not throw
The 430L Steel Melt for Continuous Casting for the grain refiner thrown.To smelt the as cast condition steel sample completed cut, roughly ground, fine grinding, after polishing, it is rotten
Lose crystal boundary out.Corrosive liquid selects 10% oxalic acid solution to be electrolysed, corrosion potentials 5V, 40~60s of etching time.
Fig. 1 (a), Fig. 1 (b) are steel sample using TiC as grain refiner respectively and do not add grain refiner steel sample
In typical metallograph.It is observed using Carl Zeiss metallographic microscope, utilizes " the average crystalline substance of GBT6394-2002 metal
Granulometry " in resection, obtain the grain size of sample under heterogeneity and content, be shown in Table 1.
The grain size rating result of 1 steel sample of table
From metallographic structure and grain size grading table it can be found that TiC can play crystal grain refinement as grain refiner
Effect, 2.4 grades when grain size number never adds fining agent are increased to 3.3 grades.
Embodiment 3
Field trash in steel after addition TiC is analyzed, field trash is carried out to the sample after polishing with scanning electron microscope
The observation of pattern.
As shown in Fig. 3 (a), (b), (c), (d), it is mingled with above in the steel using TiC as grain refiner in addition to existing
Beyond the region of objective existence, there is also TiC particle, shape is irregular quadrilateral, and size is about 6 μm.
Main inclusions are Al in 430L stainless steel containing TiC2O3-SiO2- MnO, while there is also some magnesia earthenwares
The MgO that crucible introduces.Contain SiO2Alumino-silicate it is compound be mingled with shape for circle, size is generally at 4~5 μm or so.
Claims (4)
1. a kind of grain refiner for ferritic stainless steel continuous casting, which is characterized in that its raw material composition and weight percent
Are as follows: TiC powder 0.01~0.05%, remaining is greater than 99.95% Fe powder for content；Partial size < 1 μm of the TiC powder, the Fe powder
Partial size be 10~20 μm, the grain density of TiC powder is greater than 20000/mm in the grain refiner3；Described is used for iron
The preparation method of the grain refiner of ferritic stainless steel continuous casting, includes the following steps:
(1) abrasive material: bulky grain TiC powder made from carbothermic method is placed in planetary mills and is ground, is ground to average grain diameter less than 1
μm, obtain micron-sized TiC powder；
(2) it mixes: obtained micron order TiC powder and partial size is claimed in 10~20 μm of Fe powder according to weight percent respectively
It takes, is placed in ball mill and is uniformly mixed；
(3) hip moulding: the mixed powder obtained after step (2) are mixed carries out hip moulding, hip moulding
Temperature is 1200 DEG C~1300 DEG C, and pressure is greater than 15Mpa, obtains the grain refiner for ferritic stainless steel continuous casting.
2. the grain refiner according to claim 1 for ferritic stainless steel continuous casting, which is characterized in that preparation method
The step of (2) in, incorporation time be 30~50min.
3. the application method of the grain refiner described in claim 1 for ferritic stainless steel continuous casting, which is characterized in that
The grain refiner is added in molten steel by continuous casting production process tundish station.
4. application method according to claim 3, which is characterized in that the additive amount of grain refiner is steel per ton addition
The grain refiner of 100~500g, molten steel overheat is 10~15 DEG C when addition, and addition manner is to throw.
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Families Citing this family (4)
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| CN108642241A (en) * | 2018-06-05 | 2018-10-12 | 东北大学 | A kind of ferritic stainless steel grain refiner, preparation method and application |
| CN112853039B (en) * | 2020-12-31 | 2022-05-27 | 东北大学 | Bearing steel self-uniform grain refiner and preparation method thereof |
| CN112853040B (en) * | 2020-12-31 | 2022-05-27 | 东北大学 | 440C stainless bearing steel grain refiner and preparation method thereof |
| CN114029591B (en) * | 2021-09-28 | 2023-03-14 | 材谷金带(佛山)金属复合材料有限公司 | Active flux suitable for ferrite stainless steel tungsten electrode argon arc welding base metal self-melting welding process |
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