CN108044105A - A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering - Google Patents

A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering Download PDF

Info

Publication number
CN108044105A
CN108044105A CN201711369227.3A CN201711369227A CN108044105A CN 108044105 A CN108044105 A CN 108044105A CN 201711369227 A CN201711369227 A CN 201711369227A CN 108044105 A CN108044105 A CN 108044105A
Authority
CN
China
Prior art keywords
sintering
powder
hot
silicon steel
high temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201711369227.3A
Other languages
Chinese (zh)
Inventor
丁艺
罗丰华
王冠
罗硕
李阳
白云波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201711369227.3A priority Critical patent/CN108044105A/en
Publication of CN108044105A publication Critical patent/CN108044105A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • 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
    • 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

Landscapes

  • 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

The present invention provides a kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering, reduction Fe powder and water atomization Fe powder is chosen, according to 4:6~6:4 ratio mixing, then Si powder is added, form Fe Si mixed powders.By being molded squarely base, then using uniaxial compression mode under the conditions of 920~980 DEG C, 100~160MPa 0.5~2h of hot pressed sintering, the density of green compact is made to reach 6.68~7.00g/cm3；Then powder hot-pressing sintered blank is subjected to vacuum at 1080~1180 DEG C or protection of reducing atmosphere is sintered, then multiple low-temperature diffusion-sintering and rolled thickness reduction；High temperature diffusion sintering finally is carried out at 1280~1350 DEG C, realizes homogeneous alloy, obtains 0.1~0.5mm thickness containing 4.5~6.7%Si, density >=7.34g/cm3High silicon steel band.

Description

A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering
Technical field
Preparation and manufacture field the invention belongs to metal material, and in particular to the powder hot-pressing sintering 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
The method for preparing high silicon steel band is sintered with powder hot-pressing the object of the present invention is to provide a kind of sintering of High temperature diffusion, The problem of being difficult to shape for Fe-4.5~6.7%Si alloy thin band materials, it is uniform with technical pure Fe powder and fine simple substance Si powder Mixing is molded into green compact after adding binder, then prepares certain thickness slab using powder hot-pressing sintering method, utilizes powder Last hot pressed sintering causes green density to improve the emollescence of Fe powder, and realizes slight alloying under thermal diffusion effect, Form the complex tissue of Fe particles and the high Si phases of brittleness with plastic deformation ability.Subsequently after multi-pass cold rolling-sintering Thin plate is obtained, progressively promotes the alloying of Si, is finally sintered using High temperature diffusion and obtains the fine and close high silicon steel band of homogeneous single phase.
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 adds fine Si powder as raw material powder, is formed Fe-4.5~6.7%Si mixed powders.Fine Si powder is adhered in mixed process by suitable bonding agent, dispersant In the hole of reduced iron powder surface or filling ferrous powder.Since technical pure Fe powder is the big particle with high-compressibility, mixing Occupy larger volume ratio in powder, its plastic deformation ability is not significantly reduced after adding Si powder, it can be by being molded squarely base. Uniaxial compression mode 0.5~2h of hot pressed sintering under the conditions of 920~980 DEG C, 100~160MPa is used again, makes the density of green compact Reach 6.68~7.00g/cm3.Then powder hot-pressing sintered blank is subjected to vacuum or reduction in 1080~1180 DEG C of temperature ranges Gas-protecting sintering, makes Fe powder particles metallurgical bindings, and Si and Fe realize it is partially-alloyed, formed it is fine and close, there is plasticity to become 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 shape ability.Expand subsequently through multiple cold rolling, low temperature Sintering is dissipated, the density rise of slab, plate thickness are reduced, and the alloying level of Si is also continuously improved.Finally at 1280~1350 DEG C Vacuum or protection of reducing atmosphere sintering, the homogeneous alloy of high silicon steel is realized with the help of thermal diffusion, is obtained in temperature range 0.1~0.5mm containing 4.5~6.7%Si is thick, density >=7.34g/cm3High silicon steel band.
The method 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.
With the simple substance Si powder of grain size≤3 μm, purity is more than 97%, mainly containing Fe, Al, Ca and other are inevitably miscellaneous Matter.
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 green 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 has higher compressibility and mobility, is conducive to the uniform flow of powder extrusion 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.
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, is squeezing, is not being easily caused in rolling densification process Cracking.But Si is easily absorbing oxygen, and SiO is formed on powder surface2Film, therefore in the preparation, storage and transfer process of Si powder In and follow-up batch mixing, heating, powder hot-pressing sintering process in should use inert gas shielding, used instrument is also necessary 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, 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, pre- mixed Fe powder and Si powder are weighed；It is used under inert protective atmosphere Low energy mixer mixes, and mixing velocity and time, the mitigation Fe powder that should try one's best was sent out in mixed process depending on mixing uniformity Raw processing hardening.
(3) powder hot-pressing is sintered
Square green compact is prepared using compression-moulding methods, green density is 6.32~6.49g/cm3, by green compact in 920 0.5~2h of hot pressed sintering at~980 DEG C, makes the density of green compact reach 6.68~7.00g/cm3。
Decline the plasticity of plate after hot pressed sintering in order to avoid alloying, relatively low heating has been selected before hot pressed sintering Temperature.Alloy is regarded as the composite material of simple substance Fe particles and richness Si phase compositions after sintering, possesses the high-plastic of pure Fe crystal grain Property characteristic, three point bending test show plasticity, and bending strength reaches 116~271MPa.
(4) cold rolling-sintering
It by above-mentioned hot pressed sintering 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 1080~1180 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, is gradually completing with the alloying of Si, and strip density improves, reach 7.33~ 7.47g/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 pressed sintering 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 1280~1350 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 slightly improves, and reaches 7.34~7.48g/cm3。
In step (1) mixed process absolute ethyl alcohol is added in 200~500ml/ tons of ratio.
The simple substance silica flour of grain size≤3 μm by high-energy ball milling or rushes the acquisition of rotation method in step (1).
Low energy mixer described in step (2) is conical mixer, V-arrangement batch mixer or drum mixer.
Step (2) adds that cellulose, paraffin micro mist or zinc stearate are water-insoluble as binder, and binder adds when mixing Dosage 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, bonding Fe-Si powder, the effect for enhancing 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) prepares square green compact using compression-moulding methods, is pressed using hydraulic press on the surface of 400~600MPa Under power, square green compact is obtained, green compact length and width is respectively 100~300mm, is highly 40~60mm；It is put into the oxidation of same size Aluminium compacting tool set, using hot-pressed sintering furnace, the uniaxial compression mode of 100~160MPa, under hydrogen shield effect, in 920~ 0.5~2h of hot pressed sintering at 980 DEG C, slab three point bending test shows as plasticity after hot pressed sintering, bending strength for 116~ 271MPa。
Support plate described in step (4) uses molybdenum plate, W plates, heat resisting steel, corundum or zirconia ceramics plate.
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 is by being added in the pre- mixed technical pure Fe powder of the big volumetric portion with good plasticity The fine Si powder of simple substance of certain volume ratio forms Fe-4.5~6.7Si% mixtures.After powder hot-pressing sintering, form Fine and close soft Fe particles and the composite material of hard crisp richness Si phase compositions, have higher deformation at room temperature ability.Subsequently through multi-pass Cold rolling and sintering further improve structural homogenity and compactness, then by being similar to CVD high-temperature diffusion process, realize Si's Homogenization, so as to obtain the single-phase high silicon steel band of high quality.This method realizes technical process certainly by technique and equipment Design Dynamicization, continuous production, can be mass-produced 0.1~0.5mm thickness, density >=7.34g/cm3High silicon steel band.
Description of the drawings
Fig. 1 is the three-point bending graph of blank after the powder hot-pressing of the embodiment of the present invention 1 is sintered；
Fig. 2 is metallographic structure figure after powder hot-pressing sintering-cold rolling-sintering of the embodiment of the present invention 2；
Fig. 3 is XRD diffraction curve figures after powder hot-pressing sintering-cold rolling-sintering of the embodiment of the present invention 2；
Fig. 4 is XRD diffraction curve figures after powder hot-pressing sintering-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 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 simple substance Si powder of grain size≤3 μm according to 93.3:6.7 ratio mixing, shape Into the mixed-powder of Fe-6.7%Si.The paraffin micro mist of raw material total amount 0.6%, 0.1% machine oil are added during mixing.Absolute ethyl alcohol It is added according to 200ml/ tons of amounts.Using V-arrangement batch mixer by above-mentioned powder mixing 4h.
Prepare square green compact using compression-moulding methods, surface pressing 600MPa, green compact size for 100 × 100 × 40mm, green density 6.32g/cm3。
The uniaxial compression hot pressed sintering of 100MPa, the hot pressed sintering 2h at 920 DEG C, the thickness of blank are about 36mm, density Reach 6.68g/cm3.Three point bending test shows plasticity, sees Fig. 1, and bending strength reaches 116MPa.
By above-mentioned hot pressed sintering 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 1080 DEG C of heat preservation sintering 2h in vacuum sintering furnace, plate is thick Degree is thinned to 0.49mm, and density reaches 7.33g/cm3。
1h is sintered in 1350 DEG C of Temperature Vacuums, realizes the full alloyings of Si, forms single-phase alloy, thickness 0.5mm, density reaches 7.34g/cm3, Si contents are 6.7%.
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 simple substance Si powder of grain size≤3 μm according to 95.5:4.5 ratio mixing, shape Into the mixed-powder of Fe-4.5%Si.The zinc stearate of raw material total amount 0.7%, 0.1% machine oil are added during mixing.Absolute ethyl alcohol It is added according to 400ml/ tons of amounts.Using drum mixer by above-mentioned powder mixing 6h.
Prepare square green compact using compression-moulding methods, surface pressing 400MPa, green compact size for 300 × 300 × 60mm, green density 6.49g/cm3.The uniaxial compression hot pressed sintering of 160MPa, hot pressed sintering 0.5h, blank at 980 DEG C Thickness be about 54mm, density reaches 7.00g/cm3.Three point bending test shows plasticity, and bending strength reaches 271MPa.
By above-mentioned hot pressed sintering 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 1180 DEG C of heat preservations 0.5h is tied, sheet metal thickness is thinned to 0.10mm, and density reaches 7.47g/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.
4h is sintered in 1280 DEG C of Temperature Vacuums, realizes the full alloyings of Si, forms single-phase alloy, thickness 0.1mm, density reaches 7.48g/cm3, Si contents are 4.5%.
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 simple substance Si powder of grain size≤3 μm according to 93.5:6.5 ratio mixing, shape Into 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.Using drum mixer by above-mentioned powder mixing 6h.
Prepare square green compact using compression-moulding methods, surface pressing 500MPa, green compact size for 120 × 120 × 50mm, green density 6.36g/cm3.The uniaxial compression hot pressed sintering of 150MPa, hot pressed sintering 1.5h, blank at 950 DEG C Thickness be about 46mm, density reaches 6.72g/cm3.Three point bending test shows plasticity, and bending strength reaches 156MPa.
By above-mentioned hot pressed sintering 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 7.35g/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 7.36g/cm3, Si contents are 6.5%,
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 simple substance Si powder of grain size≤3 μm according to 94.2:5.8 ratio mixing, shape Into the mixed-powder of Fe-5.8%Si.The paraffin micro mist of raw material total amount 0.6%, 0.2% machine oil are added during mixing.Absolute ethyl alcohol It is added according to 400ml/ tons of amounts.Using drum mixer by above-mentioned powder mixing 3h.
Prepare square green compact using compression-moulding methods, surface pressing 500MPa, green compact size for 180 × 180 × 50mm, green density 6.40g/cm3.The uniaxial compression hot pressed sintering of 130MPa, the hot pressed sintering 1h at 950 DEG C, blank Thickness is about 52mm, and density reaches 6.76g/cm3.Three point bending test shows plasticity, and bending strength reaches 225MPa.
By above-mentioned hot pressed sintering plate cold rolling-sintering, specific pressure-annealing schedule, which is progressively thinned, 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 7.40g/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 7.41g/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 (8)

1. a kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering, it is characterised in that including walking as follows Suddenly：
(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 mass ratio is prepared, using conical mixer, V-arrangement batch mixing Machine or drum mixer are mixed to form technical pure Fe powder basic materials, and incorporation time is 2~6h；
The simple substance Si powder of grain size≤3 μm, purity is more than 97%, mainly containing Fe, Al and Ca and other inevitable impurity；
(2) powder mixes
According to the ratio of Fe-4.5~6.7%Si, pre- mixed technical pure Fe powder and simple substance Si powder are weighed；In inert protective atmosphere It is lower to be mixed using low energy mixer；
(3) powder hot-pressing is sintered
Square green compact is prepared using compression-moulding methods, green density is 6.32~6.49g/cm3, by green compact in 920~980 0.5~2h of hot pressed sintering at DEG C makes the density of green compact reach 6.68~7.00g/cm3；
(4) cold rolling-sintering
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 30~50%, then in 1080~1180 DEG C of 0.5~2h of heat preservation sintering, after multiple cold rolling-sintering, plate in sintering furnace Thickness reach 0.1~0.5mm, density reaches 7.33~7.47g/cm3；
(5) full alloying high temperature sintering
Vacuum or restitutive protection 1~4h of atmosphere sintering in 1280~1350 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 0.1~0.5mm after densification sintering, Density reaches 7.34~7.48g/cm3。
2. the method that High temperature diffusion sintering as described in claim 1 prepares high silicon steel band with powder hot-pressing sintering, feature It is：The simple substance Si powder of grain size≤3 μm is by high-energy ball milling or rushes the acquisition of rotation method.
3. the method that High temperature diffusion sintering as described in claim 1 prepares high silicon steel band with powder hot-pressing sintering, feature It is：The low energy mixer is conical mixer, V-arrangement batch mixer or drum mixer.
4. the method that High temperature diffusion sintering as claimed in claim 2 prepares high silicon steel band with powder hot-pressing sintering, feature It is：In step (1) mixed process 200~500ml absolute ethyl alcohols are added in by ton mixed-powder.
5. the method that High temperature diffusion sintering as claimed in claim 2 prepares high silicon steel band with powder hot-pressing sintering, feature It is：It is water-insoluble as binder, the addition of binder that step (2) adds cellulose, paraffin micro mist or zinc stearate when mixing Measure total amount is no more than mixed-powder gross mass 0.8%, while add grease and absolute ethyl alcohol does passivator, rise passivation Si powder, The effect of Fe-Si powder, enhancing powder flowbility and compact strength is bonded, the additive amount total amount of passivator is total no more than mixed-powder The 2% of quality.
6. the method that High temperature diffusion sintering as described in claim 1 prepares high silicon steel band with powder hot-pressing sintering, feature It is：Step (3) prepares square green compact using compression-moulding methods, using hydraulic press 400~600MPa surface pressing Under, square green compact is obtained, green compact length and width is respectively 100~300mm, is highly 40~60mm；It is put into the aluminium oxide of same size Compacting tool set, using hot-pressed sintering furnace, the uniaxial compression mode of 100~160MPa, under hydrogen shield effect, in 920~980 0.5~2h of hot pressed sintering at DEG C, slab three point bending test shows as plasticity after hot pressed sintering, bending strength for 116~ 271MPa。
7. the method that High temperature diffusion sintering as described in claim 1 prepares high silicon steel band with powder hot-pressing sintering, feature It is：Support plate described in step (4) uses molybdenum plate, W plates, heat resisting steel, corundum or zirconia ceramics plate.
8. the method that High temperature diffusion sintering as described in claim 1 prepares high silicon steel band with powder hot-pressing sintering, feature It is：During high temperature sintering described in step (5), 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.
CN201711369227.3A 2017-12-18 2017-12-18 A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering Withdrawn CN108044105A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711369227.3A CN108044105A (en) 2017-12-18 2017-12-18 A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711369227.3A CN108044105A (en) 2017-12-18 2017-12-18 A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering

Publications (1)

Publication Number Publication Date
CN108044105A true CN108044105A (en) 2018-05-18

Family

ID=62133695

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711369227.3A Withdrawn CN108044105A (en) 2017-12-18 2017-12-18 A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering

Country Status (1)

Country Link
CN (1) CN108044105A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1273611A (en) * 1998-05-29 2000-11-15 住友特殊金属株式会社 Method for producing high silicon steel and silicon steel
CN1528921A (en) * 2003-09-25 2004-09-15 武汉理工大学 High-silica silicon-steel sheet heat treatment and multiple cold-rolling method
CN104962798A (en) * 2015-07-24 2015-10-07 北京科技大学 Method for preparing high-silicon steel by powder sleeve forming
CN107282928A (en) * 2017-07-17 2017-10-24 贵州理工学院 Powder Diffusion prepares the method and device of high-silicon steel thin strip under magnetic field

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1273611A (en) * 1998-05-29 2000-11-15 住友特殊金属株式会社 Method for producing high silicon steel and silicon steel
CN1528921A (en) * 2003-09-25 2004-09-15 武汉理工大学 High-silica silicon-steel sheet heat treatment and multiple cold-rolling method
CN104962798A (en) * 2015-07-24 2015-10-07 北京科技大学 Method for preparing high-silicon steel by powder sleeve forming
CN107282928A (en) * 2017-07-17 2017-10-24 贵州理工学院 Powder Diffusion prepares the method and device of high-silicon steel thin strip under magnetic field

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
员文杰，沈强，张联盟: "粉末轧制法制备Fe-6.5%Si硅钢片的研究", 《粉末冶金技术》 *
员文杰: "粉末轧制法制备高硅硅钢片的工艺及过程原理的研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 *
周勇: "铁、硅复合粉末的轧制成型与后续热处理", 《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》 *
张翔: "粉末冶金法制备高硅硅钢片的轧制和热处理工艺研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

Similar Documents

Publication Publication Date Title
CN107900345A (en) A kind of Powder hot isostatic pressure manufacture method of high silicon steel thin belt material
CN108097961A (en) A kind of method that High temperature diffusion sintering prepares high silicon steel band with Powder hot isostatic pressure
CN107829036A (en) A kind of powder hot-pressing sintering manufacture method of high silicon steel thin belt material
CN107999757A (en) A kind of method that powder hot-pressing sintering prepares single-phase Fe-6.5%Si silicon steel
CN107971494A (en) A kind of method that powder hot-pressing sintering prepares Fe-6.5%Si soft magnetic materials thin strips
CN108103390A (en) A kind of method that Powder hot isostatic pressure prepares single-phase Fe-6.5%Si silicon steel
CN107900347A (en) A kind of method that powder hotforging prepares high silicon steel band with High temperature diffusion sintering
CN107971495A (en) A kind of method that Powder hot isostatic pressure prepares Fe-6.5%Si soft magnetic materials thin strips
CN108097965A (en) A kind of powder extruding method for making of high silicon steel thin belt material
CN108044106A (en) A kind of method that Powder hot isostatic pressure prepares high silicon steel band with High temperature diffusion sintering
CN107855532A (en) A kind of method that powder hot-pressing sintering prepares high silicon steel thin belt material
CN107900346A (en) A kind of method that Powder hot isostatic pressure prepares high silicon steel thin belt material
CN107900348A (en) A kind of method that powder hotforging prepares single-phase Fe 6.5%Si silicon steel
CN108044107A (en) A kind of Powder hot isostatic pressure preparation method of Fe-6.5%Si soft magnetic materials thin strip
CN107900349A (en) A kind of method that powder hotforging prepares Fe 6.5%Si soft magnetic materials thin strips
CN108044105A (en) A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder hot-pressing sintering
CN107900354A (en) A kind of method that powder extruding prepares high silicon steel thin belt material
CN108080641A (en) A kind of powder rolling preparation method of Fe-6.5%Si soft magnetic materials thin strip
CN108015287A (en) A kind of method that hot pressed sintering prepares Fe-6.5%Si bands with High temperature diffusion sintering
CN108097959A (en) A kind of method that High temperature diffusion sintering prepares Fe-6.5%Si bands with hot pressed sintering
CN108044108A (en) A kind of method that powder hot-pressing sintering prepares high silicon steel band with High temperature diffusion sintering
CN107999758A (en) A kind of powder hot-pressing sintering preparation method of Fe-6.5%Si soft magnetic materials thin strip
CN108097966A (en) A kind of method that High temperature diffusion sintering prepares high silicon steel band with powder warm-rolling
CN108044100A (en) A kind of method that powder rolling prepares Fe-6.5%Si soft magnetic materials thin strips
CN107983962A (en) A kind of method that powder rolling prepares single-phase Fe-6.5%Si silicon steel

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20180518