CN108044101A - A kind of method that powder rolling prepares Fe-6.5%Si bands with diffusion-sintering - Google Patents

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

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CN108044101A
CN108044101A CN201711369181.5A CN201711369181A CN108044101A CN 108044101 A CN108044101 A CN 108044101A CN 201711369181 A CN201711369181 A CN 201711369181A CN 108044101 A CN108044101 A CN 108044101A
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powder
sintering
rolling
prepares
high temperature
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罗丰华
温家飞
唐紫薇
廖相巍
李益民
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Central South University
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18—Manufacture 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
    • 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
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Abstract

A kind of method that powder rolling prepares Fe 6.5%Si bands with diffusion-sintering, the present invention chooses reduction Fe powder and two kinds of Industrial iron powders of water atomization Fe powder, according to 4:6~6:4 ratio mixing, then the HIGH-PURITY SILICON iron powder that fine Si contents are 70~80% is added, form Fe 4.5~6.7%Si mixed powders.Vacuum or protection of reducing atmosphere sintering are carried out after powder rolling at 1060~1160 DEG C, Fe powder particles is made to realize not exclusively connection, forms the high blank plates of silicon steels of incomplete alloying porous, that there is compressibility.Subsequently through multiple cold rolling, not exclusively sintering, the density rise of slab, thickness are reduced, and the alloying level of Si is also continuously improved.It is finally sintered in 1250~1320 DEG C of temperature ranges, realizes the homogeneous alloy of high silicon steel, obtain 0.1~0.5mm thickness containing 4.5~6.7%Si, 7.34~7.50g/cm of density3High silicon steel band.

Description

A kind of method that powder rolling 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 of the high silicon steel soft magnetism band of high-performance Metallurgy sintered and rolling deformation method.
Technical background
Remanent magnetism and coercive force all very littles of soft magnetic material, i.e. hysteresis loop is very narrow, it and fundamental magnetization curve are almost It overlaps, is 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.There is no absolute predominances, such as slope in soft magnetic materials for the maximum permeability of Fe-Si alloys The maximum permeability of alloy can not reach 200000.However the manufacture of the Fe-Si lattens of Si ＜ 4.5% is at low cost, 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 increases with Si contents And reduce, it disappears substantially at about 6.3%, and<111>The magnetostriction coefficient in direction increases with Si contents and is increased, 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 the iron core of amount or large size is sent in vibrations not only causes the loss of energy, also creates noise pollution.Especially It is in the military aviations such as spacecraft, submarine and guided missile field, Fe-Si systems alloy plays particularly important role.20th century 60 Age Mo, the alloy of Si contents 6.5% are appeared in as transformer material on No. 11 airships of Apollo, are completed the mankind and are landed on the moon for the first time 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 is for the first time the study found that 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 have lower iron loss and higher magnetic conductivity.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 spends for 0.1~0.5mm, width is the No yield point 6.5%Si steel discs of 400mm.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 to alloy diffusion inside alloy is finally made to reach required content by raised 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 It asks, 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 ", and 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, 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 generate huge economic benefit and social benefit.
The content of the invention
The object of the present invention is to provide the sides that a kind of powder rolling and High temperature diffusion sintering prepare Fe-6.5%Si thin strips Method, the problem of being difficult to shape 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, is formed with compressibility powder mixture after adding binder, then is rolled using powder Method processed prepares certain thickness slab, degreasing, sintering after form porous, heterogeneous blank, by multi-pass cold rolling- Thin plate is obtained after sintering, is finally sintered using High temperature diffusion and obtains the high silicon steel band of homogeneous.
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.It will in mixed process by suitable bonding agent, dispersant Fine HIGH-PURITY SILICON iron powder is adhered in the hole of iron powder surface or filling ferrous powder.Since technical pure Fe powder is with high-compressibility Big particle, larger volume ratio is occupied in mixed powder, add fine Si contents be 70~80% HIGH-PURITY SILICON iron powder After will not significantly reduce its deformability, porous slab can be formed by powder rolling.By powder rolling slab 1060~ 1160 DEG C of temperature ranges carry out vacuum or protection of reducing atmosphere sintering, and Fe powder particles is made to realize not exclusively connection, and Si and Fe is real It is existing partially-alloyed, form the high silicon steel blank of incomplete alloying porous, that there is compressibility.Subsequently through repeatedly cold It rolls, be not exclusively sintered, the density rise of slab, plate thickness are reduced, and the alloying level of Si is also continuously improved.Finally 1250~ The homogeneous alloy of high silicon steel is realized in vacuum or protection of reducing atmosphere sintering in 1320 DEG C of temperature ranges with the help of thermal diffusion Change, obtain 0.1~0.5mm thickness containing 4.5~6.7%Si, density >=7.34g/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 Si, Mn, P, S and other are inevitable Impurity, using -100 mesh water-atomized iron powders, Fe >=99.0% in water atomization Fe powder, remaining for Si, Mn, P, S and other can not The impurity avoided, by reduction Fe powder and water atomization Fe powder according to 4:6~6:4 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.
Si contents are used as 70~80% HIGH-PURITY SILICON iron powder, grain size≤10 μm, this ferrosilicon powder except contain 70~ Beyond 80%Si, major impurity is~0.25%Al ,~0.08%Ca ,~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 during follow-up powder rolling also being mutually twisted for powder easy to implement and improve the intensity of green compact, be conducive to The stabilization of powder rolling process.Water atomization Fe powder is also a kind of widely used Industrial iron powder, has subsphaeroidal pattern, and impurity contains Amount has higher compressibility and mobility, is conducive to the uniform flow of powder rolling process course powder less than reduction Fe powder Dynamic, low impurity content is favourable to the soft magnetic characteristic of high silicon steel in water atomization Fe powder.It 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 eutectics Reaction, forms the β-FeSi with tP3 structures2With Si phase eutectic structures, it is this tissue it is very crisp, 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, Si phases, FeSi in actual tissue2 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 grain size≤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 subsequent blank toughness, cracking is not easily caused in densification process is rolled.But Fe-70~ There are still more Si phases, Si in 80%Si high purity ferrosilicons to be 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 in follow-up batch mixing, the operation of rolling Inert gas shielding should be used, used instrument must also take dehydration, drying process in advance.
On the premise of oxygen content is controlled, influence of the impurity such as Al, Ca, Mn to alloy magnetic property is little, introduces in the process The possibility of other alloying elements is also little.
(2) powder mixes
According to the ratio of Fe-4.5~6.7%Si, pre- mixed Fe powder and Fe-70~80%Si HIGH-PURITY SILICON iron powders are weighed； It is mixed under inert protective atmosphere using low energy mixer, mixing velocity and time depending on mixing uniformity, should try one's best and subtract Processing hardening occurs in mixed process for light Fe powder.
(3) powder rolling
Using two roller horizontal mills and feeding trough is tilted, is conducted oneself with dignity using powder, the frictional force feeding between roll and powder, Thickness is rolled out as 1.0~2.3mm, width is 100~240mm, and density is 6.2~6.8g/cm3Powder strip plate.
Go out the difference in roller direction by band, powder rolling can be divided into vertical, horizontal and tilt 3 kinds of forms, and feeding manner has Dead weight feeding, forced feed, pre-glued feeding etc..The width of blank is related with the width of feeding trough, and the length of blank regards production Depending on condition is permitted and is actually needed.
(4) degreasing, sintering
Powder strip plate is placed on surface to be coated in the support plate of MgO micro mists, is placed into vacuum degreasing, sintering furnace, 2~4h is kept the temperature respectively using the heating rate of 2~5 DEG C/min, and in 200 DEG C, 400 DEG C, then will heat up to 1060~1160 DEG C 2~4h of heat preservation sintering, sintered blank density are 6.3~6.9g/cm3。
Uniform equiaxed grain structure is formed after sintering.Matrix grain is about 70~120 μm, and crystal boundary has about 10~20 μm Hole, subsequent rolling and sintering can be closed.A large amount of 1~5 μm of the second phase is evenly distributed in matrix, with matrix group Good interface cohesion is woven with, i.e., the face divided does not occur.These obvious second phases are certain richness Si phases, these richness Si phases In the presence of reducing the Si contents of matrix so that matrix has high plastic deformation ability；Meanwhile with matrix group It knits good interface cohesion and Dispersed precipitate is conducive to subsequently homogenization diffusion.
Sintering temperature is too low, the connection being unfavorable between Fe powder particles and Si atoms permeatings, and sintering temperature is excessively high then can be by In the diffusion into the surface of Fe, Si element, there is coarse hole, be subsequently difficult to press, rolling densification is difficult to realize.
During sintering can powder rolling blank can be placed with multilayer, but must separate between layers, to avoid plate during sintering Base contraction causes to crack.Heating rate should not be too fast during sintering, and multistage heat preservation can be set in temperature-rise period, to realize degassing, take off The effect of fat.Reproducibility or inert gas shielding degreasing, sintering can also be taken.W, Mo, heat resisting steel etc. may be employed during sintering As support plate (or burn boat), the ceramic wafers such as corundum, zirconium oxide can also be used, but metallic plate thermal conductivity it is good and beneficial to uniformly Sintering shrinkage.
(5) cold rolling-sintering densification
By above-mentioned sintering slab rolled thickness reduction, single pass rolling reduction≤8% reaches 30 through multi- pass rolling to total reduction After~45%, in sintering furnace, 0.5~2h is re-sintered in 1060~1160 DEG C, after multiple cold rolling-sintering, the thickness of plate reaches To 0.1~0.5mm, density reaches 7.33~7.49g/cm3。
Since powder batch is porous organization, and there are deformable Fe phases, slab can bear cold-rolling deformation.Palette There is also more high Si phases in base, performance is more crisp, therefore not above 8%, accumulation total reduction reaches amount under every time rolling 8~20 passages are taken around to 30~45%.
Due to there are a large amount of holes and hard crisp phase, taking when re-sintering for 1060 DEG C~1160 DEG C, in vacuum-sintering or also Originality protective atmosphere is sintered, to realize the reparation of the closing of pores and crackle and the homogenization diffusion of a degree of Si elements.This When heating rate can be very fast, in 5~10 DEG C/min, can continuous warming, soaking time determines depending on thickness of slab, during thickness of slab >=1mm, protects The warm time is 1~2h；Thickness of slab is reduced to 0.5~1h in 0.1~1mm, soaking time.Sintered accumulation drafts reaches every time , it is necessary to be sintered 1 time again after 30~45%, 0.1~0.5mm is rolled down to from the powder base of 1.0~2.5mm, takes around and burns again Knot 4~8 times.In addition, in order to which the density of plate is made to reach 7.2g/cm3More than (about the 95% of theoretical density), it is also desirable to 4 times Above re-sinters.
By 2 cold rollings-sintered metallographic structure.Matrix is about 100 μm of grain structure, there is a small amount of tiny hole Gap.Matrix grain is there are two types of different contrasts, this is because Si contents are different and cause to corrode difference, low Si is brilliant in this kind tissue Grain is conducive to machining deformation so that the thin plate of 0.1~0.5mm of manufacture is possibly realized.
(6) high temperature sintering is homogenized
Finally vacuum or restitutive protection 1~4h of atmosphere sintering in 1250~1320 DEG C of temperature ranges, in thermal diffusion Under effect, the homogenization of Si is realized, form single-phase alloy, obtain the high silicon steel of homogeneous.The thickness of plate is almost after densification sintering It is constant, it is 0.1~0.5mm, density reaches 7.34~7.50g/cm3。
Placement sintering plate can be overlapped during high temperature sintering, but interlayer must be laid with MgO powder, and W, Mo can be used and ceramics are burnt Boat.But plate must tile placement, and tablet weight can be placed on plate, prevents from deforming in sintering process.
In addition to Si contents, content of elements such as grain size, crystal grain orientation, C etc. also has the magnetic behavior of high silicon steel Large effect can subsequently be annealed by wet hydrogen, the technological means such as normalizing treatment are controlled by.
Essence of the invention be by be 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 alloy mixtures, and powder rolling is into after slab Incomplete alloying sintering is carried out, Fe powder particles is made to realize not exclusively sintering, and Si and Fe realizations are partially-alloyed, formed more Hole, have compressibility incomplete alloying high silicon steel blank.Subsequently through multi-pass cold rolling and sintering, it is equal to improve tissue Even property and compactness, then by high-temperature diffusion process, the homogenization of Si is realized, so as to obtain the single-phase high silicon steel of complete alloying Band.This method realizes Technics Process Automation, continuous production by technique and equipment Design, it can be mass-produced 0.1~ 0.5mm is thick, 7.34~7.50g/cm of density3High silicon steel band.
Description of the drawings
Fig. 1 is the sintered metallograph of powder rolling base of the embodiment of the present invention 2；
Fig. 2 is that the plate of the embodiment of the present invention 3 passes through 2 cold rollings-sintered metallograph
Fig. 3 is XRD diffraction curves after the powder rolling base high temperature sintering of the embodiment of the present invention 4.
Specific 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 ratio is prepared, and is mixed using drum-type Material machine is mixed to form technical pure Fe powder raw materials, incorporation time 2h, is added in mixed process according to 200ml/ tons of ratio anhydrous Ethyl alcohol.
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.
Using two roller horizontal mills and feeding trough is tilted, is conducted oneself with dignity using powder, the frictional force feeding between roll and powder, The powder rolling slab of 2.5mm is rolled out, the width of slab is 100mm.The density of green compact is 6.2g/cm3。
Powder strip plate is placed on surface to be coated on the molybdenum plate of MgO micro mists, is placed into vacuum degreasing, sintering furnace.It adopts With the heating rate of 2 DEG C/min, and 4h is kept the temperature respectively in 200 DEG C, 400 DEG C.Then will heat up to 1060 DEG C of heat preservation sintering 4h.It burns It is 6.3g/cm to tie base density3。
By above-mentioned sintering slab rolled thickness reduction, single pass rolling reduction≤8% reaches 30 through multi- pass rolling to total reduction After~45%, then in vacuum sintering furnace, in 1060 DEG C of heat preservation sinterings.With 5 DEG C/min speed continuous warmings, soaking time regards plate Thickness determines, during thickness of slab >=1mm, soaking time 2h；Thickness of slab is in 0.1~1mm, soaking time 1h.Specific pressure-annealing schedule For：2.3mm → 1.6mm → 1.02mm → 0.71mm → 0.49mm, i.e., after 4 cold rollings and 3 sintering, the thickness of plate reaches 0.49mm, density reach 7.33g/cm3。
For above-mentioned cold rolling made-up belt in 1320 DEG C of vacuum-sintering 1h, it is about 0.50mm, density 7.34g/cm to obtain thickness3, Si Content is the 6.7% high silicon steel of single-phase homogeneous.
Embodiment 2
By the water atomization Fe powder of the reduction Fe powder of -100 mesh and -100 mesh according to 5:6 ratio is prepared, and is mixed using drum-type Material machine is mixed to form technical pure Fe powder raw materials, incorporation time 3h, is added in mixed process according to 400ml/ tons of ratio anhydrous Ethyl alcohol.
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.
Using two roller horizontal mills and feeding trough is tilted, is conducted oneself with dignity using powder, the frictional force feeding between roll and powder, The powder rolling slab of 1.0mm is rolled out, the width of slab is 240mm.The density of green compact is 6.8g/cm3。
Powder strip plate is placed on surface to be coated on the molybdenum plate of MgO micro mists, is placed into vacuum degreasing, sintering furnace.It adopts With the heating rate of 5 DEG C/min, and 2h is kept the temperature respectively in 200 DEG C, 400 DEG C.Then will heat up to 1160 DEG C of heat preservation sintering 2h.It burns It is 6.9g/cm to tie base density3。
Uniform equiaxed grain structure is formed after sintering, sees Fig. 1.Matrix grain is about 70~120 μm, and crystal boundary presence about 10~ 20 μm of hole, subsequent rolling and sintering can be closed.A large amount of 1~5 μm of the second phase is evenly distributed in matrix, with Matrix has good interface cohesion, i.e., the face divided does not occur.These obvious second phases are certain richness Si phases, these are rich The presence of Si phases reduces the Si contents of matrix so that matrix has high plastic deformation ability；Meanwhile with The good interface cohesion of matrix and Dispersed precipitate are conducive to subsequently homogenization diffusion.
By above-mentioned sintering slab rolled thickness reduction, single pass rolling reduction≤8% reaches 30 through multi- pass rolling to total reduction After~45%, then in vacuum sintering furnace, in 1160 DEG C of heat preservation sinterings.With 10 DEG C/min speed continuous warmings, soaking time is 1h.Specifically pressure-annealing schedule is：1.0mm → 0.65mm → 0.39mm → 0.25mm → 0.17mm → 0.13mm → 0.10mm, I.e. after 6 cold rollings and 5 sintering, the thickness of plate reaches 0.10mm, and density reaches 7.49g/cm3。
For above-mentioned cold rolling made-up belt in 1250 DEG C of vacuum-sintering 4h, it is about 0.10mm, density 7.50g/cm to obtain thickness3, Si Content is the 4.5% high silicon steel of single-phase homogeneous.
Embodiment 3
By the water atomization Fe powder of the reduction Fe powder of -100 mesh and -100 mesh according to 6:4 ratio is prepared, and is mixed using drum-type Material machine is mixed to form technical pure Fe powder raw materials, incorporation time 4h, is added in mixed process according to 500ml/ tons of ratio anhydrous Ethyl alcohol.
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.
Using two roller horizontal mills and feeding trough is tilted, is conducted oneself with dignity using powder, the frictional force feeding between roll and powder, The powder rolling slab of 1.6mm is rolled out, the width of slab is 150mm.The density of green compact is 6.3g/cm3。
Powder strip plate is placed on surface to be coated on the corundum plate of MgO micro mists, the degreasing of hydrogen tube furnace is placed into, burns Knot.Using the heating rate of 3 DEG C/min, and 2h, 400 DEG C of heat preservation 3h are kept the temperature at 200 DEG C.Then it will heat up to 1150 DEG C of heat preservations and burn Tie 3h.Sintered blank density is 6.36g/cm3。
By above-mentioned sintering slab rolled thickness reduction, single pass rolling reduction≤8% reaches 30 through multi- pass rolling to total reduction After~45%, then in hydrogen tube furnace, in 1150 DEG C of heat preservation sintering 1h.With 6 DEG C/min speed continuous warmings.Specific pressure- Annealing schedule is：1.6mm → 1.08mm → 0.70mm → 0.45mm → 0.27mm, i.e., after 4 cold rollings and 3 sintering, plate Thickness reach 0.27mm, density reaches 7.38g/cm3。
See Fig. 2 by 2 cold rollings-sintered metallographic structure, matrix is about 100 μm of grain structure, is existed a small amount of thin Small hole.Matrix grain is there are two types of different contrasts, this is because Si contents are different and cause to corrode difference, in this kind tissue Low Si crystal grain is conducive to machining deformation so that the thin plate of 0.1~0.5mm of manufacture is possibly realized.
For above-mentioned cold rolling made-up belt in 1300 DEG C of vacuum-sintering 2h, it is about 0.27mm, density 7.39g/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 ratio is prepared, and is mixed using drum-type Material machine is mixed to form technical pure Fe powder raw materials, incorporation time 6h, is added in mixed process according to 500ml/ tons of ratio anhydrous Ethyl alcohol.
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.
Using two roller horizontal mills and feeding trough is tilted, is conducted oneself with dignity using powder, the frictional force feeding between roll and powder, The powder rolling slab of 2.0mm is rolled out, the width of slab is 180mm.The density of green compact is 6.4g/cm3。
Powder strip plate is placed on surface to be coated on the corundum plate of MgO micro mists, the degreasing of hydrogen tube furnace is placed into, burns Knot.Using the heating rate of 4 DEG C/min, and 3h, 400 DEG C of heat preservation 2h are kept the temperature at 200 DEG C.Then it will heat up to 1130 DEG C of heat preservations and burn Tie 2h.Sintered blank density is 6.46g/cm3。
By above-mentioned sintering slab rolled thickness reduction, single pass rolling reduction≤8% reaches 30 through multi- pass rolling to total reduction After~45%, then in hydrogen tube furnace, in 1130 DEG C of heat preservation sintering 0.5h.With 8 DEG C/min speed continuous warmings.2.0mm→ 1.3mm → 0.96mm → 0.72mm → 0.46mm → 0.32mm → 0.21mm, i.e., after 7 cold rollings and 6 sintering, the thickness of plate Degree reaches 0.21mm, and density reaches 7.41g/cm3.In 1280 DEG C of vacuum-sintering 2h, obtain thickness is about above-mentioned cold rolling made-up belt 0.22mm, density 7.42g/cm3, Si contents are 5.8%, and the XRD analysis figure of final plate is shown in Fig. 3, are that single-phase homogeneous is high Silicon steel.

Claims (8)

1. a kind of method that powder rolling prepares Fe-6.5%Si thin strips with High temperature diffusion sintering, it is characterised in that including following Step：
(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 is Si, Mn, P, S and other are inevitable Impurity, will reduction Fe powder and water atomization Fe powder according to 4:6~6:4 ratio is prepared, using conical mixer, V-arrangement batch mixer Or drum mixer is mixed to form technical pure Fe powder basic materials, incorporation time is 2~6h；
Si contents are used as 70~80% HIGH-PURITY SILICON iron powder, grain size≤10 μm, major impurity is~0.25%Al ,~0.08% Ca ,~0.02%C, remaining is Fe；
(2) powder mixes
According to the ratio of Fe-4.5~6.7%Si, pre- mixed Fe powder and Fe-70~80%Si HIGH-PURITY SILICON iron powders are weighed；Lazy Property protective atmosphere under using low energy mixer mix；
(3) powder rolling
Using two roller horizontal mills and feeding trough is tilted, is conducted oneself with dignity using powder, the frictional force feeding between roll and powder, rolled Go out thickness for 1.0~2.3mm, width is 100~240mm, and density is 6.2~6.8g/cm3Powder strip plate；
(4) degreasing, sintering
Powder strip plate is placed on surface to be coated in the support plate of MgO micro mists, is placed into vacuum degreasing, sintering furnace, using 2 The heating rate of~5 DEG C/min, and 2h~4h is kept the temperature respectively in 200 DEG C, 400 DEG C, it then will heat up to 1060~1160 DEG C of guarantors Temperature 2~4h of sintering, sintered blank density are 6.3~6.9g/cm3；
(5) cold rolling-sintering densification：
By above-mentioned sintering slab rolled thickness reduction, single pass rolling reduction≤8%, reach 30 through multi- pass rolling to total reduction~ After 45%, in sintering furnace, 0.5~2h is re-sintered in 1060~1160 DEG C, after multiple cold rolling-sintering, the thickness of plate reaches 0.1~0.5mm, density reach 7.33~7.49g/cm3；
(6) high temperature sintering is homogenized
Vacuum or restitutive protection 1~4h of atmosphere sintering in 1250~1320 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 7.34~7.50g/cm3。
2. the method that powder rolling as described in claim 1 prepares Fe-6.5%Si thin strips with High temperature diffusion sintering, special Sign is：The absolute ethyl alcohol of 200~500ml is added in step (1) mixed process according to mixed-powder per ton.
3. the method that powder rolling as described in claim 1 prepares Fe-6.5%Si thin strips with High temperature diffusion sintering, special Sign is：With high-energy ball milling or rush rotation method obtain grain size≤3 μm simple substance Si powder.
4. the method that powder rolling as described in claim 1 prepares Fe-6.5%Si thin strips with High temperature diffusion sintering, special Sign is：Low energy mixer described in step (2) is conical mixer, V-arrangement batch mixer or drum mixer.
5. the method that powder rolling as described in claim 1 prepares Fe-6.5%Si thin strips with High temperature diffusion sintering, special Sign is：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 passivation Si powder, viscous The effect of Fe-Si powder, enhancing powder flowbility and compact strength is connect, the additive amount total amount of passivator is no more than the total matter of mixed-powder The 2% of amount.
6. the method that powder rolling as described in claim 1 prepares Fe-6.5%Si thin strips with High temperature diffusion sintering, special Sign is：Step (5) is sintered, by 5~10 when re-sintering for 1060~1160 DEG C under vacuum-sintering or restitutive protection's atmosphere DEG C/min continuous warmings, during thickness of slab >=1mm, soaking time is 1~2h；Thickness of slab in 0.1~1mm, soaking time is reduced to 0.5~ 1h after sintered accumulation drafts reaches 30~45% every time, is sintered 1 time, is rolled down to from the powder base of 1.0~2.3mm again 0.1~0.5mm, it is necessary to be sintered 4~8 times again.
7. the method that powder rolling as described in claim 1 prepares Fe-6.5%Si thin strips with High temperature diffusion sintering, special Sign is：Overlapping places sintering plate during high temperature sintering, and interlayer is laid with MgO powder.
8. the method that powder rolling as described in claim 1 prepares Fe-6.5%Si thin strips with High temperature diffusion sintering, special Sign is：Support plate described in step (4) burns boat using W, Mo, corundum or zirconia ceramics.
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