CN108044107A - A kind of Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip - Google Patents

A kind of Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip Download PDF

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CN108044107A
CN108044107A CN201711369232.4A CN201711369232A CN108044107A CN 108044107 A CN108044107 A CN 108044107A CN 201711369232 A CN201711369232 A CN 201711369232A CN 108044107 A CN108044107 A CN 108044107A
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powder
hot isostatic
sintering
soft magnetic
magnetic materials
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罗丰华
周浩钧
李益民
白云波
张德敏
吴博天
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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
    • 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
    • B22F3/12Both compacting and sintering
    • B22F3/14Both compacting and sintering simultaneously
    • B22F3/15Hot isostatic pressing
    • 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
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

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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 hot isostatic pressure prepares single-phase Fe 6.5%Si silicon steel, for the present invention using water atomization Fe powder, Si powder is raw material powder, forms Fe Si mixed powders.It adds bonding agent and dispersant is uniform, then soft iron jacket is used, in 1075~1185 DEG C of temperature ranges, under the hot isostatic pressing effect of 100~200MPa, obtain the green compact of even compact, by the high Si phase compositions of the α Fe crystal grain and brittleness of poor Si, there is plastic deformation ability, green density reaches 6.76~7.08g/cm3.It is sintered by multiple cold rolling, low temperature diffusion, density rise, thickness are reduced, and are finally sintered in 1280~1350 DEG C of temperature ranges, the homogeneous alloy of high silicon steel is realized with the help of thermal diffusion, it is thick to obtain 0.1~0.5mm containing 4.5~6.7%Si, density >=7.32g/cm3High silicon steel band.

Description

A kind of Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip
Technical field
Preparation and manufacture field the invention belongs to metal material, and in particular to the Powder hot isostatic pressure of high silicon steel thin belt material With the method for rolling deformation.
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
A kind of Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip, for Fe-4.5~6.7% The problem of Si alloy thin band materials are difficult to shape uniformly is mixed with fine simple substance Si powder with water atomization Fe powder, utilizes hot isostatic pressing Hot mastication effect and the characteristics of uniform pressure, prepare highdensity uniformity slab, and realized under thermal diffusion effect Partially-alloyed, being formed has the α-Fe crystal grain of poor Si of plastic deformation ability and the heterogeneous structure of the high Si phases of brittleness.Follow-up warp It is further thinned after crossing multi-pass cold rolling-sintering, is finally sintered using High temperature diffusion and obtains the high silicon steel band of homogeneous single phase.
The present invention is achieved by the following technical solutions:Subsphaeroidal water atomization Fe powder, fine Si powder are used as original Feed powder end, forms Fe-4.5~6.7%Si mixed powders.It is uniformly mixed after adding a small amount of bonding agent, dispersant, then using soft Iron jacket in 1075~1175 DEG C of temperature ranges, under the hot isostatic pressing effect of 100~200MPa, obtains pressure uniformly, fine and close Base.Green density reaches 6.76~7.08g/cm3.Under the heat effect of hot isostatic pressing and pressure effect, Fe powder particles obtain Metallurgical binding, and incomplete diffusion has occurred in Si elements, and it is brilliant to form α-Fe fine and close, with the poor Si of plastic deformation ability The heterogeneous structure of grain and the high Si phases of brittleness.It is sintered subsequently through multiple cold rolling, low temperature diffusion, the density rise of slab, plate thickness It reduces, the alloying level of Si is also continuously improved.Finally vacuum or protection of reducing atmosphere in 1275~1345 DEG C of temperature ranges The homogeneous alloy of high silicon steel is realized in sintering with the help of thermal diffusion, obtains 0.1~0.5mm thickness containing 4.5~6.7%Si, Density >=7.32g/cm3High silicon steel band.
The method of the present invention specifically comprises the following steps:
(1) raw material powder prepares
Using -100 mesh water-atomized iron powders, Fe >=99.0% in water-atomized iron powder, remaining for Si, Mn, P, S and other can not The impurity avoided, with the simple substance Si of grain size≤3 μm, purity is more than 97%, mainly containing Fe, Al, Ca and other are inevitably miscellaneous Matter.
Water atomization Fe powder is a kind of widely used Industrial iron powder, has subsphaeroidal pattern, impurity content is less than reduction Fe Powder has higher compressibility and mobility, is conducive to the Uniform Flow of powder extrusion process course powder.Water atomization Fe powder In low impurity content it is favourable to the soft magnetic characteristic of high silicon steel.
The property of simple substance Si is very crisp, it is easy to be refined by Mechanical Crushing technique.The elemental silicon for choosing 3 μm of grain size < is favourable In the realization of subsequently homogenization diffusion-sintering;And hole that tiny Si is formed in blank, brittle interface are also tiny, play The Strengthening and Toughening effect of structure refinement, is conducive to improve subsequent blank toughness, does not easily cause cracking in densification process.But Si Oxygen is easily absorbing, SiO is formed on powder surface2Film, therefore in the preparation, storage and transfer process of Si powder, Yi Jihou Inert gas shielding should be used during continuous batch mixing, heating, Powder hot isostatic pressure, used instrument must also be taken de- in advance Water, drying process.
On the premise of oxygen content is controlled, influence of the impurity such as other Al, Ca, Mn to alloy magnetic property is little, in the process The possibility for introducing other alloying elements is also little.
(2) powder mixes
According to the ratio of Fe-4.5~6.7%Si, water atomization Fe powder and Si powder are weighed, it is fully mixed under inert protective atmosphere It closes uniform.
(3) Powder hot isostatic pressure
Using soft iron jacket, in 1075~1175 DEG C of temperature ranges, under the hot isostatic pressing effect of 100~200MPa, protect The pressure time is 0.5~2h, obtains green compact uniformly, fine and close, and green density reaches 6.76~7.08g/cm3
(4) cold rolling-sintering
It by above-mentioned hot isostatic pressing plate cold rolling-sintering, is progressively thinned, single pass rolling reduction≤8%, through multi- pass rolling to always After reduction ratio reaches 30~50%, then in 1075~1175 DEG C of 0.5~2h of heat preservation sintering, multiple cold rolling-sintering in sintering furnace Afterwards, the thickness of plate reaches 0.1~0.5mm, the alloying of Si progressively into rear, strip density to 7.30~7.43g/cm3
There are a large amount of deformable Fe phases in blank, slab can bear cold-rolling deformation.But there is also more in slab High Si phases, performance is more crisp, therefore amount cannot be too high under every time rolling, and accumulation total reduction reaches 30~50%, takes around 8 ~25 passages.
Since existing hard crisp phase, cold deformation process can form some micro-cracks.In order to realize the closing of pores and crackle It repairs and a degree of Si elements homogenization is spread.Cold rolling reduction accumulation needs to be sintered 1 again to a certain extent afterwards It is secondary, 0.1~0.5mm is rolled down to from 36~54mm hot isostatic pressing plates, takes around and is sintered 12~20 times again.
Sintering temperature is too low, is unfavorable for the metallurgical binding of Fe powder particles and Si element thermal diffusions;And sintering temperature is excessively high 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 or vacuum-sintering.W, Mo, heat resisting steel etc. can be used during sintering as support Plate (or burning boat), can also use the ceramic wafers such as corundum, zirconium oxide, but metallic plate thermal conductivity is good, and 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 apparent separating phenomenon, illustrate there are 2 kinds of different Fe phases of Si solid solubility, wherein must Have that the Si contents in a kind of Fe phases are low, there is plastic deformation ability.
(5) full alloying high temperature sintering
Vacuum or restitutive protection 1~4h of atmosphere sintering in 1275~1345 DEG C of temperature ranges, in the effect of thermal diffusion Under, it realizes the full alloyings of Si, forms 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 is increased to 7.32~7.46g/cm3
The simple substance silica flour of grain size≤3 μm described in step (1) is by high-energy ball milling or rushes the acquisition of rotation method.
The low energy mixer is conical mixer, V-arrangement batch mixer or drum mixer.
100~300mm of length and width is processed into step (3) and by blank, thickness is 36~54mm squares;Hot isostatic pressing base The three point bending test of material shows plasticity, and bending strength is 399~590MPa.
Add cellulose, paraffin micro mist or zinc stearate water-insoluble binder during mixing, the additive amount total amount of binder is not It more than the 0.5% of mixed-powder gross mass, while adds grease and absolute ethyl alcohol does passivator, plays passivation Si powder, bonding Fe-Si The effect of powder, enhancing powder flowbility and compact strength, the additive amount total amount of passivator are no more than mixed-powder gross mass 2%.
Support plate described in step (4) uses molybdenum plate, W plates, heat resisting steel, 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 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 is by being with the addition of certain body in the water atomization Fe powder of the big volumetric portion with good plasticity The fine Si powder of simple substance of product ratio, forms Fe-4.5~6.7%Si mixed powders.High density, Gao Jun are obtained by hot isostatic pressing It is even.Incomplete alloying occurs under the heat effect of hot isostatic pressing, obtains one kind by plasticity Fe crystal grain and the high Si phases group of brittleness Into composite material.Subsequently through multi-pass cold rolling and sintering, structural homogenity and compactness are improved, then is burnt by High temperature diffusion Knot realizes the homogenization of Si, so as to obtain the single-phase 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 >=7.32g/cm3High silicon steel Band.
Description of the drawings
Fig. 1 be the embodiment of the present invention 1 Powder hot isostatic pressure after blank three-point bending graph;
Fig. 2 is metallographic structure figure after Powder hot isostatic pressure-cold rolling-sintering of the embodiment of the present invention 2;
Fig. 3 is XRD diffraction curve figures after Powder hot isostatic pressure-cold rolling-sintering of the embodiment of the present invention 2;
Fig. 4 is XRD diffraction curve figures after Powder hot isostatic pressure-cold rolling-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 -100 mesh and the simple substance Si powder of grain size≤3 μm according to 93.3:6.7 ratio mixing, forms The mixed-powder of Fe-6.7%Si.The paraffin micro mist of raw material total amount 0.4%, 0.1% machine oil are added during mixing.Absolute ethyl alcohol is pressed It is added according to 200ml/ tons of amounts.
After above-mentioned powder is sufficiently mixed, using soft iron jacket, in 1075 DEG C of temperature ranges, the hot isostatic pressing of 200MPa Under effect, dwell time 2h obtains green compact uniformly, fine and close.Jacket is removed with machine-tooled method, and blank is processed into 36 The square of × 100 × 100mm.Green density reaches 6.73g/cm3.Three point bending test test bending strength reaches 399MPa, See Fig. 1, and show plasticity.
By above-mentioned hot isostatic pressing plate cold rolling-sintering, progressively it is thinned.Specifically pressure-annealing schedule is:36mm→24mm→ 17mm→12mm→9.5mm→7.2mm→5mm→3.5mm→2.4mm→1.6mm→1.02mm→1.02mm→0.71mm→ 0.49mm is sintered through 13 cold rollings and 12 times.
For multi-pass cold rolling to after 30~50%, then in 1075 DEG C of heat preservation sintering 2h in vacuum sintering furnace, plate is thick Degree is thinned to 0.49mm, and density reaches 7.35g/cm3
4h is sintered in 1275 DEG C of Temperature Vacuums, realizes the full alloyings of Si, forms single-phase alloy, thickness 0.5mm, density reaches 7.37g/cm3, Si contents are 6.7%.
Embodiment 2
By the water atomization Fe powder of -100 mesh and the simple substance Si powder of grain size≤3 μm according to 95.5:4.5 ratio mixing, forms The mixed-powder of Fe-4.5%Si.The zinc stearate of raw material total amount 0.3%, 0.1% machine oil are added during mixing.Absolute ethyl alcohol is pressed It is added according to 400ml/ tons of amounts.
After above-mentioned powder is sufficiently mixed, using soft iron jacket, in 1175 DEG C of temperature ranges, the hot isostatic pressing of 100MPa Under effect, dwell time 0.5h obtains green compact uniformly, fine and close.Jacket is removed with machine-tooled method, and blank is processed into The square of 54 × 300 × 300mm.Green density reaches 7.05g/cm3.Three point bending test test bending strength reaches 590MPa。
By above-mentioned hot isostatic pressing plate cold rolling-sintering, progressively it is thinned.Specifically pressure-annealing schedule is:54mm→36mm→ 36mm→24mm→17mm→12mm→9.5mm→7.2mm→5mm→3.5mm→2.4mm→1.6mm→1.02mm→ 1.02mm → 0.71mm → 0.49mm → 0.39mm → 0.25mm → 0.17mm → 0.13mm → 0.10mm, i.e., through 20 cold rollings and 19 sintering.
Multi-pass cold rolling is to after 30~50% total reductions, then is burnt in hydrogen shield sintering furnace in 1175 DEG C of heat preservations 0.5h is tied, sheet metal thickness is thinned to 0.10mm, and density reaches 7.48g/cm3
The texture of coarse crystal containing the second phase is formed after sintering, sees Fig. 2.X-ray diffraction Discriminating materials are heterogeneous Fe (Si) phase, as seen in Figure 3, body-centred cubic several characteristic peaks have apparent separating phenomenon, illustrate there are Si solid solubility it is different 2 Kind Fe phases, wherein must have, the Si contents in a kind of Fe phases are low, have plastic deformation ability.
1h is sintered in 1345 DEG C of Temperature Vacuums, realizes the full alloyings of Si, forms single-phase alloy, thickness 0.1mm, density reaches 7.51g/cm3, Si contents are 4.5%.
Embodiment 3
By the water atomization Fe powder of -100 mesh and the simple substance Si powder of grain size≤3 μm according to 93.5:6.5 ratio mixing, forms The mixed-powder of Fe-6.5%Si.The paraffin micro mist of addition raw material total amount 0.4% during mixing, 0.2% methylcellulose, 0.1% machine oil.Absolute ethyl alcohol is added according to 400ml/ tons of amount.
After above-mentioned powder is sufficiently mixed, using soft iron jacket, in 1120 DEG C of temperature ranges, the hot isostatic pressing of 160MPa Under effect, dwell time 1.5h obtains green compact uniformly, fine and close.Jacket is removed with machine-tooled method, and blank is processed into The square of 46 × 200 × 200mm.Green density reaches 6.86g/cm3.Three point bending test test bending strength reaches 492MPa。
By above-mentioned hot isostatic pressing plate cold rolling-sintering, progressively it is thinned.Specifically pressure-annealing schedule is:46mm→36mm→ 24mm→17mm→12mm→9.5mm→7.2mm→5mm→3.5mm→2.4mm→1.6mm→1.02mm→1.02mm→ 0.71mm → 0.49mm → 0.39mm → 0.27mm is sintered through 16 cold rollings and 15 times.
Multi-pass cold rolling is to after 30~50% total deformations, then is burnt in nitrogen protective sintering stove in 1120 DEG C of heat preservations 1h is tied, sheet metal thickness is thinned to 0.27mm, and density reaches 7.39g/cm3
2h is sintered in 1320 DEG C of Temperature Vacuums, realizes the full alloyings of Si, forms single-phase alloy, thickness 0.27mm, density reaches To 7.41g/cm3, Si contents are 6.5%,
Embodiment 4
By the water atomization Fe powder of -100 mesh and the simple substance Si powder of grain size≤3 μm according to 94.2:5.8 ratio mixing, forms The mixed-powder of Fe-5.8%Si.The paraffin micro mist of raw material total amount 0.3%, 0.02% machine oil are added during mixing.Absolute ethyl alcohol It is added according to 400ml/ tons of amounts.
After above-mentioned powder is sufficiently mixed, using soft iron jacket, in 1120 DEG C of temperature ranges, the hot isostatic pressing of 150MPa Under effect, dwell time 1h obtains green compact uniformly, fine and close.Jacket is removed with machine-tooled method, and blank is processed into 52 The square of × 160 × 160mm.Green density reaches 6.88g/cm3.Three point bending test test bending strength reaches 509MPa.
By above-mentioned hot isostatic pressing plate cold rolling-sintering, progressively it is thinned.Specifically pressure-annealing schedule is:52mm→39mm→ 26mm→18mm→13mm→10.5mm→8.2mm→5mm→3.2mm→2.4mm→2.0mm→1.3mm→0.90mm→ 0.63→0.43mm→0.32mm→0.21mm.It is sintered through 17 cold rollings and 16 times.
Multi-pass cold rolling is to after 30~50% total deformations, then is burnt in hydrogen shield sintering furnace in 1150 DEG C of heat preservations 1h is tied, sheet metal thickness is thinned to 0.21mm, and density reaches 7.43g/cm3
2h is sintered in 1300 DEG C of Temperature Vacuums, realizes the full alloyings of Si, forms single-phase alloy, thickness 0.21mm, density reaches To 7.44g/cm3, Si contents are 5.8%, and the XRD analysis figure of final plate is shown in Fig. 4, are the high silicon steel of single-phase homogeneous.

Claims (7)

1. a kind of Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip, it is characterised in that including following step Suddenly:
(1) raw material powder prepares
Using -100 mesh water-atomized iron powders, Fe >=99.0% in water-atomized iron powder, remaining is Si, Mn, P, S and other are inevitable Impurity, with the simple substance Si of grain size≤3 μm, purity is more than 97%, mainly containing Fe, Al, Ca and other inevitable impurity;
(2) powder mixes
According to the ratio of Fe-4.5~6.7%Si, water atomization Fe powder and Si powder are weighed, is sufficiently mixed under inert protective atmosphere It is even;
(3) Powder hot isostatic pressure
Using soft iron jacket, in 1075~1175 DEG C of temperature ranges, under the hot isostatic pressing effect of 100~200MPa, during pressurize Between for 0.5~2h, obtain green compact uniformly, fine and close, green density reaches 6.76~7.08g/cm3
(4) cold rolling-sintering
It is progressively thinned, single pass rolling reduction≤8%, above-mentioned hot isostatic pressing plate cold rolling-sintering through under multi- pass rolling to stagnation pressure After rate reaches 30~50%, then in 1075~1175 DEG C of 0.5~2h of heat preservation sintering, after multiple cold rolling-sintering, plate in sintering furnace The thickness of material reaches 0.1~0.5mm, the alloying of Si progressively into rear, strip density to 7.30~7.43g/cm3
(5) full alloying high temperature sintering
Vacuum or restitutive protection 1~4h of atmosphere sintering in 1275~1345 DEG C of temperature ranges, it is real under the action of thermal diffusion The existing full alloyings of Si, form single-phase alloy, obtain the high silicon steel of homogeneous, and the thickness of plate is almost unchanged after densification sintering, is 0.1 ~0.5mm, density are increased to 7.32~7.46g/cm3
2. the Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip as described in claim 1, feature It is:The simple substance silica flour of grain size≤3 μm described in step (1) is by high-energy ball milling or rushes the acquisition of rotation method.
3. the Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip as described in claim 1, feature It is:The low energy mixer is conical mixer, V-arrangement batch mixer or drum mixer.
4. the Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip as described in claim 1, feature It is:100~300mm of length and width is processed into step (3) and by blank, thickness is 36~54mm squares;Hot isostatic pressing blank Three point bending test shows plasticity, and bending strength is 399~590MPa.
5. the Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip as described in claim 1, feature It is:Add cellulose, paraffin micro mist or zinc stearate water-insoluble binder during mixing, the additive amount total amount of binder is no more than The 0.5% of mixed-powder gross mass, while add grease and absolute ethyl alcohol does passivator, rise passivation Si powder, bonding Fe-Si powder, Enhance the effect of powder flowbility and compact strength, the additive amount total amount of passivator is no more than the 2% of mixed-powder gross mass.
6. the Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip as described in claim 1, feature It is:Support plate described in step (4) uses molybdenum plate, W plates, heat resisting steel, corundum or zirconia ceramics plate.
7. the Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip as described in claim 1, feature It is:During high temperature sintering described in step (6), overlapping places sintering plate, and interlayer is laid with MgO powder, and plate tiling is placed, in plate Tablet weight is placed on material, prevents from deforming in sintering process.
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