CN107999767A - A kind of method that powder extruding prepares Fe-6.5%Si bands with diffusion-sintering - Google Patents

A kind of method that powder extruding prepares Fe-6.5%Si bands with diffusion-sintering Download PDF

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CN107999767A
CN107999767A CN201711369194.2A CN201711369194A CN107999767A CN 107999767 A CN107999767 A CN 107999767A CN 201711369194 A CN201711369194 A CN 201711369194A CN 107999767 A CN107999767 A CN 107999767A
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powder
sintering
diffusion
extrusion
bands
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丁艺
罗丰华
黄小琴
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Central South University
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Central South University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • B22F1/0003
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1003Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007Atmosphere
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • B22F2003/208Warm or hot extruding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

A kind of method that powder extruding prepares Fe 6.5%Si bands with diffusion-sintering, chooses reduction Fe powder and water atomization Fe powder, according to 4:6~6:4 mixing, then the HIGH-PURITY SILICON iron powder that Si contents are 70~80% is added, form Fe 4.5~6.7%Si mixed powders.It is molded squarely base; it is heated to 950~1050 DEG C and realizes Fe phase austenitizings; slab is hot extruded into the deflection that extrusion ratio is 8~16; vacuum or protection of reducing atmosphere sintering are carried out at 1070~1170 DEG C again; Fe powder particles is realized metallurgical binding, then multiple cold rolling, low temperature diffusion sintering, finally sintered in 1275~1335 DEG C of vacuum or protection of reducing atmosphere; realize the homogeneous alloy of high silicon steel, obtain 0.1~0.5mm thickness, density >=7.40g/cm containing 4.5~6.7%Si3High silicon steel band.

Description

A kind of method that powder extruding prepares Fe-6.5%Si bands with diffusion-sintering
Technical field
Preparation and manufacture field the invention belongs to metal material, and in particular to the powder metallurgy of high silicon steel thin belt material is burnt The method of knot, hot extrusion and rolling deformation.
Technical background
Remanent magnetism and coercive force all very littles of soft magnetic material, i.e. hysteresis curve is very narrow, it and fundamental magnetization curve are almost Overlap, be mainly used for the iron core of inductance coil, transformer, relay and motor.Fe-Si alloys maximum permeability is sent out with Si contents Changing, respectively Si mass percent it is (the same below) for 2% and 6.5% nearby there is the peak of two maximum permeabilities Value, respectively reaches 10000 and 25000.The maximum permeability of Fe-Si alloys does not have absolute predominance, such as slope in soft magnetic materials The maximum permeability of alloy can not reach 200000.But the Fe-Si lattens of Si < 4.5% manufacture cost is low, therefore Silicon steel sheet is also known as electrical sheet or silicon steel thin slice, is a kind of very important magnetic material.
And Si>When 4.5%, below 540 DEG C of temperature B can occur for Fe-Si alloys2The eutectoid decomposition reaction of ordered phase, it is raw Into the unordered phases of α-Fe and DO3Ordered phase so that alloy becomes fragile and is difficult to deform.
For iron Si system alloy of the Si contents between 4.5~6.7%, commonly referred to as high silicon steel, wherein silicone content 6.5% High silicon steel it is mostly important.Its reason is Fe-Si alloy grains edge<100>The magnetostriction coefficient in direction is with the increase of Si contents And reduce, disappear substantially at about 6.3%, and<111>The magnetostriction coefficient in direction increases and increases with Si contents, about When 6.1% with<100>The magnetostriction coefficient in direction is equal so that high silicon steel shows excellent low in higher frequency operation Iron loss characteristic.
The transformer of normal operation can occur continuous uniform " drone " sound, this is because alternating current by transformer around Group when, in the core between generate periodically variable alternating flux, cause iron core magnetostriction and shake the sound sent.Greatly The sound that amount or large-scale iron core are sent in vibrations not only causes the loss of energy, also creates noise pollution.Especially It is to play particularly important role in the military aviation such as spacecraft, submarine and guided missile field, Fe-Si systems alloy.20th century 60 Age Mo, the alloy of Si contents 6.5% are appeared on No. 11 airships of Apollo as transformer material, are completed the mankind and are landed on the moon first Heroic undertaking.As it can be seen that high silicon steel is the environment-friendly type soft magnetic materials of a kind of consumption reduction of function admirable, noise reduction.
Compared to other alloys, the research and development process of high silicon steel is relatively very long.Late 1920s A.Schulze studies discovery first, and the iron Si system alloy of silicone content 6.5% has the almost nil characteristic of magnetostriction coefficient. In the 1980s, professor K.I.Arail etc. has found the high silicon steel alloy low compared to traditional Si content in exchange dynamic magnetic field In there is the magnetic conductivity of lower iron loss and higher.Hereafter between many decades, in order to overcome the brittleness of high silicon steel, in technology of preparing side There are many trials in face.As the special rolled method of jacket or temperature control, rapid solidification method, chemical vapour deposition technique (CVD method), Plasma chemical vapor deposition (PCVD methods), hot dipping ooze a diffusion annealing method, powder metallurgic method, microalloying and are modified Etc. various methods.
Wherein CVD is the successful example of comparison.NKK companies of Japan in 1988 have produced thickness for the first time using CVD technology It is the No yield point 6.5%Si steel discs of 400mm to spend for 0.1~0.5mm, width.Phase early 1990s, global first commercialization Can realize that the CVD production lines of continuous siliconising are developed, the product size of production can reach 0.1~0.3mm × 600mm。
The principle of CVD is:Under specific temperature conditions, silicon-containing gas (SiCl4) can react generation Fe- with silicon strip Si compounds, and alloy is reached required content to alloy diffusion inside by elevated furnace temperature.Although oneself uses this Technology realizes small-scale industrialized production, but its scale and yield all can not much meet the need in international soft magnetic materials market Ask, and this preparation method technical process is sufficiently complex, energy consumption and of high cost, operating environment and its severe, it is impossible to meet ring Guaranteed request.
High silicon steel is " the steel art work ", its technology of preparing is all always and everywhere state-of-the-art steel and iron manufacturing technology, and It is the hot spot of development and exploitation.For 6.5%Si high silicon steel, its excellent magnetic performance and wide application prospect are even more to inhale Draw scientific worker and carry out substantial amounts of research-and-development activity.The development of preparation process and ripe and can be cost-effectively Production, is that 6.5%Si high silicon steel move towards to be commercialized widely applied key, also the always emphasis of research work.Once grope Go out simple, economic, effective, ripe preparation process, will just produce huge economic benefit and social benefit.
The content of the invention
The side of Fe-6.5%Si thin strips is prepared with High temperature diffusion sintering the object of the present invention is to provide a kind of extruding of powder Method, the problem of being difficult to shaping for the Fe-Si alloy thin band materials of 4.5~6.7%Si contents, using technical pure Fe powder and Si contents as 70~80% HIGH-PURITY SILICON iron powder is raw material, and extruding green compact are molded into after adding binder, then using powder hot-extrusion method system For certain thickness slab is gone out, acted on using the large deformation of hot extrusion and cause the raising of extruded stock density, structure refinement, and in thermal expansion Dissipate and realize partially-alloyed under effect, form the α-Fe crystal grain of the poor Si of plastic deformation ability and the multiphase group of the high Si phases of brittleness Knit.Thin plate subsequently is obtained after multi-pass cold rolling-sintering, is finally sintered using High temperature diffusion and obtains the high silicon strip of homogeneous single phase Material.
The present invention is achieved by the following technical solutions:Reduction Fe powder and two kinds of Industrial iron powders of water atomization Fe powder are chosen, According to 4:6~6:4 ratio mixing, forms technical pure Fe powder basic materials, then it is 70~80% to add fine Si contents HIGH-PURITY SILICON iron powder, forms Fe-4.5~6.7%Si mixed powders.By suitable bonding agent, dispersant by fine HIGH-PURITY SILICON Iron powder is adhered in mixed process in the hole of iron powder surface or filling ferrous powder.Since technical pure Fe powder is with height The big particle of compressibility, occupies larger volume ratio in mixed powder, its plasticity is not significantly reduced after adding HIGH-PURITY SILICON iron powder Deformability, can be by being molded squarely base.It is heated to 950~1050 DEG C and realizes Fe phase austenitizings, is 8 with extrusion ratio ~16 deflection is hot extruded into slab.Then powder extruding slab is subjected to vacuum in 1070~1170 DEG C of temperature ranges or gone back Former gas-protecting sintering, makes Fe powder particles realize metallurgical binding, and Si and Fe realize it is partially-alloyed, formed densification, have The high silicon steel blank of heterogeneous structure of the high Si phases of α-Fe crystal grain and brittleness of the poor Si of plastic deformation ability.Subsequently through multiple cold rolling, Low temperature diffusion sinters, and the density rise of slab, plate thickness are reduced, and the alloying level of Si is also continuously improved.Finally 1275~ Vacuum or protection of reducing atmosphere sintering in 1335 DEG C of temperature ranges, realize the homogeneous alloy of high silicon steel with the help of thermal diffusion Change, obtain 0.1~0.5mm thickness containing 4.5~6.7%Si, density >=7.4g/cm3High silicon steel band.
The method of the present invention specifically comprises the following steps:
(1) raw material powder prepares
Using -100 mesh reduced iron powders, Fe >=98.5% in Fe powder is reduced, remaining is the impurity such as Si, Mn, P, S, middle particle diameter Positioned at 75~106 μm;Using -100 mesh water-atomized iron powders, Fe >=99.0% in water atomization Fe powder, remaining is miscellaneous for Si, Mn, P, S etc. Matter.Fe powder and water atomization Fe powder will be reduced according to 4:6~6:4 mass ratio is prepared, using conical mixer, V-arrangement batch mixer or Drum mixer is mixed to form technical pure Fe powder basic materials, and incorporation time is 2~6h.
The Si contents of refining are used as 70~80% HIGH-PURITY SILICON iron powder, particle diameter≤10 μm, this ferrosilicon powder except containing Beyond 70~80%Si, major impurity is~0.25%Al ,~0.08%Ca and~0.02%C, remaining is Fe.
Reduced iron powder is a kind of widely used Industrial iron powder, has irregular porous pattern, micro- beneficial to storing, adhering to Fine silica powder, and in follow-up powder extrusion process also being mutually twisted for powder easy to implement and improve the intensity of pressed compact, be conducive to The stabilization of powder extrusion process.Water atomization Fe powder is also a kind of widely used Industrial iron powder, has subsphaeroidal pattern, and impurity contains Amount is less than reduction Fe powder, compressibility and mobility with higher, is conducive to the uniform flow of powder extrusion process course powder Dynamic, low impurity content is favourable to the soft magnetic characteristic of high silicon steel in water atomization Fe powder.Will two kinds of reduction Fe powder and water atomization Fe powder Industrial iron powder, according to 4:6~6:4 ratio mixing, forms technical pure Fe powder basic materials, and it is each to be conducive to two kinds of straight iron powders of performance From advantage, be also relatively common method in industrial production iron-base part.
Fe-70~80%Si high purity ferrosilicons are in process of setting in addition to primary silicon crystal grain, and at 1207 DEG C, there are eutectic Reaction, forms the β-FeSi with tP3 structures2It is very crisp with Si phase eutectic structures, this tissue, it is easy to pass through Mechanical Crushing Technique refines.Fe-70~80%Si high purity ferrosilicons are crushed to≤10 μm of ferrosilicon powder, the Si phases in its actual tissue, FeSi2 It is mutually more tiny, be conducive to the thermal diffusion homogenization of Si elements during subsequent high temperature sintering, form homogeneous Fe-6.5%Si single-phase alloys. Meanwhile 20~30%Fe present in powder can effectively reduce the degree of oxidation of Si, be conducive to improve the product matter of high silicon steel Amount.
By Fe-70~80%Si high purity ferrosilicons Mechanical Crushing to particle diameter≤10 μm, be conducive to it and be adhered to reduction Fe powder Surface is filled in the hole of reduction Fe powder, tiny Si, FeSi2The mutually Dispersed precipitate in blank, plays structure refinement Strengthening and Toughening acts on, and is conducive to improve follow-up blank toughness, cracking is not easily caused in densification process is rolled.But Fe-70~ More Si phases are still suffered from 80%Si high purity ferrosilicons, Si is easily absorbing oxygen, and SiO is formed in exposed Si phase surfaces2Film, Therefore in the preparation, storage and transfer process of Fe-70~80%Si HIGH-PURITY SILICON iron powders, and follow-up batch mixing, powder hot extrusion, Inert gas shielding should be used in the operation of rolling, used instrument must also take dehydration, drying process in advance.
On the premise of oxygen content is controlled, influence of the impurity such as other Al, Ca, Mn to alloy magnetic property is little, during The possibility for introducing other alloying elements is also little.
(2) powder mixes
According to the ratio of Fe-4.5~6.7%Si, pre- mixed technical pure Fe powder and fine Fe-70~80%Si high are weighed Pure silicon iron powder;Using conical mixer, V-arrangement batch mixer or drum mixer mixing under inert protective atmosphere;
(3) powder extrudes
Square pressed compact is prepared using compression-moulding methods, green density is 6.38~6.57g/cm3;Using square extruding Cylinder, extrusion ratio are 8~16, using sintered-carbide die, lubricant are done with machine oil and glass dust, by molding square billet in nitrogen before extruding Be heated to 950~1050 DEG C under gas shielded effect, keep the temperature 2~4h, extrusion cylinder and extrusion die 400~600 DEG C of preheating insulations 1~ 2h, implements hot extrusion, the density of slab is 6.83~7.15g/cm after hot extrusion3
(4) sinter
Hot extrusion pressing plate is placed on surface to be coated with the support plate of MgO micro mists, is placed into sintering furnace.Using 2~5 DEG C/programming rate of min, it is warming up to 1070~1170 DEG C of 2~4h of heat preservation sintering.Sintered blank density is 7.25~7.39g/cm3。 Compared with extruded stock density, density slightly reduces.
Sintering temperature is too low, is unfavorable for metallurgical binding and the Si element thermal diffusions of Fe powder particles;And sintering temperature is excessive then Si elements can be caused quickly to spread, cause crystal grain excessive high hardness, embrittlement, follow-up rolling deformation is difficult to realize.
Take reproducibility, inert gas shielding sintering.Can be used during sintering W, Mo, heat resisting steel etc. as support plate (or Burn boat), the ceramic wafers such as corundum, zirconium oxide can also be used, but metallic plate thermal conductivity is good, and it is beneficial to Even Sintering.
The texture of coarse crystal containing the second phase is formed after sintering.X-ray diffraction Discriminating materials are heterogeneous Fe (Si) Phase, body-centred cubic several characteristic peaks have obvious separating phenomenon, illustrate there are 2 kinds of different Fe phases of Si solid solubility, wherein must There are the Si contents in a kind of Fe phases low, there is plastic deformation ability.
(5) cold rolling-sintering densification
By above-mentioned sintering slab, progressively cold rolling-sintering is thinned, single pass rolling reduction≤8%, through multi- pass rolling to stagnation pressure After lower rate reaches 30~45%, then in 1070~1170 DEG C of 0.5~2h of heat preservation sintering in sintering furnace.After multiple cold rolling-sintering, The thickness of plate reaches 0.1~0.5mm, and density reaches 7.39~7.50g/cm3
Cold-rolling deformation can be born since there are deformable Fe phases, slab in blank.But there is also more in slab High Si phases, its performance is more crisp, therefore for amount not above 8%, accumulation total reduction reaches 30~45%, about needs under every time rolling Want 8~20 passages.
Due to existing hard crisp phase, it is necessary to take and keep the temperature vacuum-sintering or restitutive protection's gas again at 1070~1170 DEG C Atmosphere sinters, and the closing of pores and the reparation of crackle are produced in cold-rolled process to realize, and a degree of Si elements homogenization expands Dissipate., it is necessary to sinter 1 time again, from the hot extrusion of 2.5~5.0mm after the accumulation drafts after sintering reaches 30~45% every time Plate is rolled down to 0.1~0.5mm, takes around and sinters 6~10 times again.
(6) high temperature sintering is homogenized
Vacuum or restitutive protection 1~4h of atmosphere sintering in 1275~1335 DEG C of temperature ranges, in the effect of thermal diffusion Under, realize the homogenization of Si, form single-phase alloy, obtain the high silicon steel of homogeneous.The thickness of plate is almost unchanged after densification sintering, For 0.1~0.5mm, density slightly reduces, and reaches 7.40~7.51g/cm3
In step (1) mixed process absolute ethyl alcohol is added in 200~500ml/ tons of ratio.
The HIGH-PURITY SILICON iron powder of particle diameter≤10 μm is by high-energy ball milling or rushes the acquisition of rotation method.
Step (2) adds cellulose, paraffin micro mist or the water-insoluble binder of zinc stearate, the additive amount of binder when mixing Total amount is no more than the 0.8% of mixed-powder gross mass, while adds grease and absolute ethyl alcohol does passivator, plays the high Si iron of passivation Powder, bonding Fe-Si powder, the effect for strengthening powder flowbility and compact strength, the additive amount total amount of passivator are no more than mixed powder The 2% of last gross mass.
Step (3) uses the square extrusion cylinder of 40 × 120mm, and extrusion die is 5~2.5mm × 120mm, corresponding extruding score Not Wei 8~16, using sintered-carbide die, do lubricant with machine oil and glass dust, protect molding square billet in nitrogen before extruding It is heated to 950~1050 DEG C under effect, 2~4h, extrusion cylinder and extrusion die is kept the temperature in 600 DEG C of preheating insulation 2h, using 300 tons of pressures Machine implements hot extrusion, and three point bending test shows plasticity, and bending strength is 119~196MPa.
Support plate described in step (4) uses corundum or zirconia ceramics plate.
During high temperature sintering described in step (6), overlapping places sintering plate, and interlayer is laid with MgO powder, and plate tiling is placed, Tablet weight is placed on plate, prevents from deforming in sintering process.
In addition to Si contents, content of element such as grain size, crystal grain orientation, C etc. also has the magnetic behavior of high silicon steel Large effect, can subsequently be annealed, the means such as normalizing treatment are controlled by by wet hydrogen.
Essence of the invention be by with the addition of in the technical pure Fe powder of the big volumetric portion with good plasticity granularity≤ 10 μm of Fe-70~80%Si high-purity powders, form Fe-4.5~6.7%Si mixed powders.Using hot extrusion obtain high density, High uniformity slab.The element alloyed degree of slab Si is low, its microscopic structure is by high-ductility Fe phases and brittleness richness Si phase groups Into, there is high cold deformation ability, can be by multi-pass cold rolling and sintering, raising structural homogenity and compactness, then high temperature expand Sintering is dissipated, the homogenization of Si is realized, so as to obtain the high silicon steel band of high quality.This method is real by technique and equipment Design Existing Technics Process Automation, continuous production, can be mass-produced 0.1~0.5mm thickness, density >=7.4g/cm3High silicon strip Material.
Brief description of the drawings
Fig. 1 is the three-point bending curve map of blank after the powder of the embodiment of the present invention 1 extrudes;
Fig. 2 is metallographic structure figure after powder extruding-cold rolling-sintering of the embodiment of the present invention 2;
Fig. 3 is XRD diffraction curve figures after powder extruding-cold rolling-sintering of the embodiment of the present invention 2;
Fig. 4 is XRD diffraction curve figures after powder extruding-cold rolling-high temperature sintering of the embodiment of the present invention 4.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Embodiment 1
By the water atomization Fe powder of the reduction Fe powder of -100 mesh and -100 mesh according to 4:6 mass ratio is prepared, using drum-type Batch mixer is mixed to form technical pure Fe powder raw materials, incorporation time 2h, and nothing is added according to 200ml/ tons of ratio in mixed process Water-ethanol.
By well pre-mixed technical pure Fe powder and the Fe-80%Si high-purity powders of granularity≤10 μm according to 91.625:8.375 Ratio mixing, form the mixed-powder of Fe-6.7%Si.The paraffin micro mist of addition raw material total amount 0.6% during mixing, 0.1% Machine oil.Absolute ethyl alcohol is added according to 200ml/ tons of amount.Using V-arrangement batch mixer by above-mentioned powder mixing 4h.
Square pressed compact is prepared using compression-moulding methods, the length and width of pressed compact is respectively 120mm and 80mm, is highly 40mm, uses surface pressing to be suppressed for the pressure of 600MPa, and the total output pressure of press is 576 tons.The green density of acquisition is 6.38g/cm3
Using the square extrusion cylinder of 40 × 120mm, extrusion die is respectively 5 × 120mm, and corresponding extrusion ratio is 8.Will before extruding Molding square billet is heated to 950 DEG C under nitrogen protective effect, keeps the temperature 4h.Extrusion cylinder and extrusion die are in 600 DEG C of preheating insulation 2h.Adopt Implement hot extrusion with 300 tons of press, the density of slab is 6.83g/cm after hot extrusion3, three point bending test shows plasticity, sees Fig. 1, bending strength 119MPa.
Using the programming rate of 2 DEG C/min, 1070 DEG C of heat preservation sintering 2h are warming up to.Sintered blank density is 7.25g/cm3.Burn The texture of coarse crystal containing the second phase is formed after knot.
By above-mentioned sintering slab, progressively cold rolling-sintering is thinned, single pass rolling reduction≤8%, through multi- pass rolling to stagnation pressure After lower rate reaches 30~45%, then in 1070 DEG C of heat preservation sintering 2h in sintering furnace.Specifically pressure-annealing schedule is:5mm→ 3.5mm → 2.4mm → 1.6mm → 1.02mm → 0.71mm → 0.49mm, i.e., after 6 cold rollings and 5 sintering, the thickness of plate Reach 0.49mm, density reaches 7.39g/cm3
1h finally is sintered in 1335 DEG C of Temperature Vacuums, under the action of thermal diffusion, the homogenization of Si is realized, forms single-phase conjunction Gold, obtains the high silicon steel of homogeneous.The thickness of plate is almost unchanged after densification sintering, is 0.49mm, and density reaches 7.40g/cm3
Embodiment 2
By the water atomization Fe powder of the reduction Fe powder of -100 mesh and -100 mesh according to 5:6 mass ratio is prepared, using drum-type Batch mixer is mixed to form technical pure Fe powder raw materials, incorporation time 3h, and nothing is added according to 400ml/ tons of ratio in mixed process Water-ethanol.
By well pre-mixed technical pure Fe powder and the Fe-70%Si high-purity powders of granularity≤10 μm according to 93.57:6.42 Ratio mixes, and forms the mixed-powder of Fe-4.5%Si.The zinc stearate of raw material total amount 0.7%, 0.1% machine are added during mixing Oil.Absolute ethyl alcohol is added according to 400ml/ tons of amount.Using drum mixer by above-mentioned powder mixing 6h.
Square pressed compact is prepared using compression-moulding methods, the length and width of pressed compact is respectively 120mm and 80mm, is highly 40mm, uses surface pressing to be suppressed for the pressure of 600MPa, and the total output pressure of press is 576 tons.The green density of acquisition is 6.57g/cm3
Using the square extrusion cylinder of 40 × 120mm, extrusion die is 2.5 × 120mm, and corresponding extrusion ratio is 16.Will before extruding Molding square billet is heated to 1050 DEG C under nitrogen protective effect, keeps the temperature 2h.Extrusion cylinder and extrusion die are in 600 DEG C of preheating insulation 2h. Implement hot extrusion using 300 tons of press, the density of slab is 7.15g/cm after hot extrusion3, three point bending test shows plasticity, Bending strength is 196MPa.
Using the programming rate of 2 DEG C/min, 1170 DEG C of heat preservation sintering 2h are warming up to.Sintered blank density is 7.39g/cm3.Burn The texture of coarse crystal containing the second phase is formed after knot, sees Fig. 2.X-ray diffraction Discriminating materials are heterogeneous Fe (Si) phase, such as Fig. 3 findings, body-centred cubic several characteristic peaks have obvious separating phenomenon, illustrate there are 2 kinds of different Fe phases of Si solid solubility, its In must have the Si contents in a kind of Fe phases low, there is plastic deformation ability.
By above-mentioned sintering slab, progressively cold rolling-sintering is thinned, single pass rolling reduction≤8%, through multi- pass rolling to stagnation pressure After lower rate reaches 30~45%, then in 1170 DEG C of heat preservation sintering 0.5h in sintering furnace.After multiple cold rolling-sintering, the thickness of plate Degree reaches 0.1mm, and density reaches 7.43g/cm3.Specifically cold rolling-sintering schedule is:2.5mm→1.85mm→1.39mm→ 1.15mm → 0.89mm → 0.65mm → 0.39mm → 0.25mm → 0.17mm → 0.13mm → 0.10mm, i.e., through 10 cold rollings and After 9 sintering, the thickness of plate reaches 0.10mm, and density reaches 7.50g/cm3
4h finally is sintered in 1275 DEG C of Temperature Vacuums, forms the high silicon steel of single-phase homogeneous that Si contents are 4.5%, thickness is 0.1mm, density reach 7.51g/cm3
Embodiment 3
By the water atomization Fe powder of the reduction Fe powder of -100 mesh and -100 mesh according to 6:4 mass ratio is prepared, using drum-type Batch mixer is mixed to form technical pure Fe powder raw materials, incorporation time 4h, and nothing is added according to 500ml/ tons of ratio in mixed process Water-ethanol.
By well pre-mixed technical pure Fe powder and the Fe-76%Si high-purity powders of granularity≤10 μm according to 91.45:8.55 Ratio mixes, and forms the mixed-powder of Fe-6.5%Si.The paraffin micro mist of raw material total amount 0.4%, 0.2% first are added during mixing Base cellulose, 0.1% machine oil.Absolute ethyl alcohol is added according to 400ml/ tons of amount.Using drum mixer by above-mentioned powder Mix 6h.
Square pressed compact is prepared using compression-moulding methods, the length and width of pressed compact is respectively 120mm and 80mm, is highly 40mm, uses surface pressing to be suppressed for the pressure of 600MPa, and the total output pressure of press is 576 tons.The green density of acquisition is 6.41g/cm3
Using the square extrusion cylinder of 40 × 120mm, extrusion die is 4 × 120mm, and corresponding extrusion ratio is 10.By mould before extruding Pressure square billet is heated to 1000 DEG C under nitrogen protective effect, keeps the temperature 3h.Extrusion cylinder and extrusion die are in 600 DEG C of preheating insulation 2h.Adopt Implement hot extrusion with 300 tons of press, the density of slab is 6.85g/cm after hot extrusion3, bending strength 178MPa.
Using the programming rate of 3 DEG C/min, 1120 DEG C of heat preservation sintering 2h are warming up to.Sintered blank density is 7.26g/cm3
By above-mentioned sintering slab, progressively cold rolling-sintering is thinned, and specific cold rolling-sintering schedule is:4.0mm→2.8mm→ 2.0mm → 1.40mm → 1.08mm → 0.70mm → 0.45mm → 0.27mm, i.e., after 7 cold rollings and 6 sintering, the thickness of plate Degree reaches 0.27mm, and density reaches 7.40g/cm3
For above-mentioned cold rolling made-up belt in 1295 DEG C of vacuum-sintering 2h, it is about 0.27mm, density 7.41g/cm to obtain thickness3, Si Content is the 6.5% high silicon steel of single-phase homogeneous.
Embodiment 4
By the water atomization Fe powder of the reduction Fe powder of -100 mesh and -100 mesh according to 5:5 mass ratio is prepared, using drum-type Batch mixer is mixed to form technical pure Fe powder raw materials, incorporation time 6h, and nothing is added according to 500ml/ tons of ratio in mixed process Water-ethanol.
By well pre-mixed technical pure Fe powder and the Fe-72%Si high-purity powders of granularity≤10 μm according to 91.05:8.95 Ratio mixes, and forms the mixed-powder of Fe-5.8%Si.The paraffin micro mist of raw material total amount 0.6%, 0.2% machine are added during mixing Oil.Absolute ethyl alcohol is added according to 400ml/ tons of amount.Using drum mixer by above-mentioned powder mixing 3h.
Square pressed compact is prepared using compression-moulding methods, the length and width of pressed compact is respectively 120mm and 80mm, is highly 40mm, uses surface pressing to be suppressed for the pressure of 600MPa, and the total output pressure of press is 576 tons.The green density of acquisition is 6.43g/cm3
Using the square extrusion cylinder of 40 × 120mm, extrusion die is respectively 3.2 × 120mm, and corresponding extrusion ratio is 12.5.Squeeze Molding square billet is heated to 1020 DEG C under nitrogen protective effect before pressure, keeps the temperature 4h.Extrusion cylinder and extrusion die are protected in 600 DEG C of preheatings Warm 2h.Implement hot extrusion using 300 tons of press, the density of slab is 6.87g/cm after hot extrusion3, bending strength 176MPa.
Using the programming rate of 4 DEG C/min, 1120 DEG C of heat preservation sintering 2h are warming up to.Sintered blank density is 7.27g/cm3
By above-mentioned sintering slab, progressively cold rolling-sintering is thinned, single pass rolling reduction≤8%, through multi- pass rolling to stagnation pressure After lower rate reaches 30~45%, then in 1120 DEG C of heat preservation sintering 1h in sintering furnace.After multiple cold rolling-sintering, the thickness of plate Reach 0.22mm, density reaches 7.43g/cm3.Specifically cold rolling-sintering schedule is:3.2mm→2.4mm→2.0mm→1.3mm→ 0.96mm → 0.72mm → 0.46mm → 0.32mm → 0.21mm, i.e., after 9 cold rollings and 8 sintering, the thickness of plate reaches 0.21mm, density reach 7.41g/cm3
For above-mentioned cold rolling made-up belt in 1305 DEG C of vacuum-sintering 2h, it is about 0.22mm, density 7.42g/cm to obtain thickness3, Si Content is 5.8%, and the XRD analysis figure of its final plate is shown in Fig. 3, is the high silicon steel of single-phase homogeneous.

Claims (7)

1. a kind of method that powder extruding prepares Fe-6.5%Si bands with diffusion-sintering, specifically comprises the following steps:
(1) raw material powder prepares
Using -100 mesh reduced iron powders, Fe >=98.5% in Fe powder is reduced, remaining is Si, Mn, P, S and other are inevitably miscellaneous Matter;Using -100 mesh water-atomized iron powders, Fe >=99.0% in water atomization Fe powder, remaining for Si, Mn, P, S and and other can not keep away The impurity exempted from, by reduction Fe powder and water atomization Fe powder according to 4:6~6:4 mass ratio is prepared, and is mixed using conical mixer, V-arrangement Material machine or drum mixer are mixed to form technical pure Fe powder basic materials, and incorporation time is 2~6h;
The Si contents for using refining are for 70~80% HIGH-PURITY SILICON iron powder, particle diameter≤10 μm, the major impurity of HIGH-PURITY SILICON iron powder ~0.25%Al ,~0.08%Ca and~0.02%C, remaining is Fe;
(2) powder mixes
According to the ratio of Fe-4.5~6.7%Si, pre- mixed technical pure Fe powder and Fe-70~80%Si high purity ferrosilicons are weighed Powder;Using conical mixer, V-arrangement batch mixer or drum mixer mixing under inert protective atmosphere;
(3) powder extrudes
Square pressed compact is prepared using compression-moulding methods, green density is 6.38~6.57g/cm3;Using square extrusion cylinder, squeeze Pressure ratio is 8~16, using sintered-carbide die, does lubricant with machine oil and glass dust, protects molding square billet in nitrogen before extruding 950~1050 DEG C are heated under shield effect, keep the temperature 2~4h, extrusion cylinder and extrusion die in 400~600 DEG C of 1~2h of preheating insulation, Implement hot extrusion, the density of slab is 6.83~7.15g/cm after hot extrusion3
(4) sinter
Hot extrusion pressing plate is placed on surface to be coated with the support plate of MgO micro mists, is placed into sintering furnace, using 2~5 DEG C/min Programming rate, be warming up to 1070~1170 DEG C of 2~4h of heat preservation sintering, sintered blank density is 7.25~7.39g/cm3
(5) cold rolling-sintering densification
By above-mentioned sintering slab, progressively cold rolling-sintering is thinned, single pass rolling reduction≤8%, through multi- pass rolling to total reduction After reaching 30~45%, then in sintering furnace after 1070~1170 DEG C of 0.5~2h of heat preservation sintering, multiple cold rolling-sintering, plate Thickness reach 0.1~0.5mm, density reaches 7.39~7.50g/cm3
(6) high temperature sintering is homogenized
Vacuum or restitutive protection 1~4h of atmosphere sintering in 1275~1335 DEG C of temperature ranges, it is real under the action of thermal diffusion The homogenization of existing Si, forms single-phase alloy, obtains the high silicon steel of homogeneous, and the thickness of plate is 0.1~0.5mm after densification sintering, Density reaches 7.40~7.51g/cm3
2. the method that powder extruding as claimed in claim 1 prepares Fe-6.5%Si bands with diffusion-sintering, it is characterised in that: In step (1) mixed process absolute ethyl alcohol is added in 200~500ml/ tons of ratio.
3. the method that powder extruding as claimed in claim 1 prepares Fe-6.5%Si bands with diffusion-sintering, it is characterised in that: The HIGH-PURITY SILICON iron powder of particle diameter≤10 μm is by high-energy ball milling or rushes the acquisition of rotation method.
4. the method that powder extruding as claimed in claim 1 prepares Fe-6.5%Si bands with diffusion-sintering, step (2) mixing When add cellulose, paraffin micro mist or the water-insoluble binder of zinc stearate, the additive amount total amount of binder is no more than mixed-powder The 0.8% of gross mass, while add grease and absolute ethyl alcohol does passivator, play the high Si iron powders of passivation, bonding Fe-Si powder, enhancing The effect of powder flowbility and compact strength, the additive amount total amount of passivator are no more than the 2% of mixed-powder gross mass.
5. the method that powder extruding as claimed in claim 1 prepares Fe-6.5%Si bands with diffusion-sintering, it is characterised in that: Using the square extrusion cylinder of 40 × 120mm in step (3), extrusion die is 5~2.5mm × 120mm, and corresponding extrusion ratio is respectively 8 ~16;Using sintered-carbide die, lubricant is done with machine oil and glass dust, implements hot extrusion, three-point bending using 300 tons of press Experiment shows plasticity, and bending strength is 119~196MPa.
6. the method that powder extruding as claimed in claim 1 prepares Fe-6.5%Si bands with diffusion-sintering, it is characterised in that: Support plate described in step (4) uses molybdenum plate, W plates, heat resisting steel, corundum or zirconia ceramics plate.
7. the method that powder extruding as claimed in claim 1 prepares Fe-6.5%Si bands with diffusion-sintering, it is characterised in that: During high temperature sintering described in step (6), overlapping places sintering plate, and interlayer is laid with MgO powder, and plate tiling is placed, on plate Tablet weight is placed, prevents from deforming in sintering process.
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