CN108097968A - A kind of method that powder tape casting prepares single-phase Fe-6.5%Si silicon steel - Google Patents

A kind of method that powder tape casting prepares single-phase Fe-6.5%Si silicon steel Download PDF

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CN108097968A
CN108097968A CN201711368366.4A CN201711368366A CN108097968A CN 108097968 A CN108097968 A CN 108097968A CN 201711368366 A CN201711368366 A CN 201711368366A CN 108097968 A CN108097968 A CN 108097968A
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powder
sintering
silicon steel
temperature
phase
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罗丰华
王冠
闫彦倬
白云波
李益民
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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
    • 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
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • 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
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • 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

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  • 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 tape casting prepares single-phase Fe 6.5%Si silicon steel, for the present invention using reduction Fe powder, Si powder is raw material, forms Fe 4.5~6.7%Si mixed powders.Solvent, dispersant, bonding agent and plasticizer are added in mixed powder again; finely dispersed stable slurry is made; biscuit is made on casting machine again; powder curtain coating shaping slab is carried out to vacuum or protection of reducing atmosphere sintering at 1080~1180 DEG C; Fe powder particles is made to realize not exclusively sintering; and Si and Fe realizes partially-alloyed, the high silicon steel blank of porous, with compressibility the incomplete alloying of formation.It through multiple cold rolling, not exclusively sintering, is finally sintered in 1280~1350 DEG C of vacuum or protection of reducing atmosphere, realizes the homogeneous alloy of high silicon steel, 0.1~0.5mm of the acquisition containing 4.5~6.7%Si is thick, density >=7.34g/cm3High silicon steel band.

Description

A kind of method that powder tape casting prepares single-phase Fe-6.5%Si silicon steel
Technical field
Preparation and manufacture field the invention belongs to functional metal material, and in particular to the powder stream of high silicon steel thin belt material Prolong the method for shaping and 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 object of the present invention is to provide a kind of method that powder tape casting prepares single-phase Fe-6.5%Si silicon steel, for The problem of Fe-Si alloy thin band materials of 4.5~6.7%Si contents are difficult to shape, it is equal with reduced iron powder and fine simple substance silica flour Even mixing is prepared certain thickness biscuit using powder curtain coating forming method, is formed after degreasing, sintering porous, non-equal The blank of matter.Fe crystal grain containing substantial amounts of non-alloying in blank, has good plasticity, by multi-pass cold rolling-sintering After obtain thin plate, finally using High temperature diffusion be sintered obtain the high silicon steel band of homogeneous.
The present invention is achieved by the following technical solutions：Using the reduction Fe powder of irregular pattern, fine Si powder is Raw material powder forms Fe-4.5~6.7%Si mixed powders.Solvent, dispersant, bonding agent, increasing are added in mixed powder again The ingredients such as agent are moulded, finely dispersed stable slurry is made, then certain thickness biscuit is made on casting machine.Tape casting is made Biscuit in powder particle distributing homogeneity it is high, while fine Si powder adheres to reduced iron powder surface or is filled out in mixed process It fills in the hole of iron powder.Since reduction Fe powder is the big particle with high-compressibility, larger volume is occupied in mixed powder Than not significantly reducing its deformability after adding Si powder.By powder curtain coating shaping slab 1080~1180 DEG C of temperature ranges into Row vacuum or protection of reducing atmosphere sintering, make Fe powder particles realize not exclusively sintering, and Si and Fe realizations are partially-alloyed, formed The high silicon steel blank of incomplete alloying porous, that there is compressibility.Subsequently through multiple cold rolling, not exclusively sintering, slab Density rise, plate thickness reduce, the alloying level of Si is also continuously improved.It is finally true in 1280~1350 DEG C of temperature ranges The sintering of empty or protection of reducing atmosphere is realized the homogeneous alloy of high silicon steel with the help of thermal diffusion, is obtained containing 4.5~6.7% 0.1~0.5mm of Si is thick, 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 reduced iron powder, remaining is Si, Mn, P, S and other are inevitable Impurity, the simple substance Si powder of grain size≤3 μm, purity be more than 97%, mainly containing Fe, Al and Ca and other inevitable impurity.
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 subsequently curtain coating, in deformation process also being mutually twisted for powder easy to implement and improve intensity.
The property of simple substance Si is very crisp, it is easy to be refined by Mechanical Crushing technique.The elemental silicon for choosing grain size≤3 μm 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, cracking is not easily caused in densification process is rolled. But Si is easily absorbing oxygen, and SiO is formed on powder surface2Film, therefore in the preparation, storage and transfer process of Si powder, with And inert gas shielding should be used in follow-up batch mixing, curtain coating, deformation process, used instrument must also take in advance dehydration, 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 ingredients, passivation, slurry prepare
According to the ratio of Fe-4.5~6.7%Si, reduction Fe powder and fine Si powder are weighed, forms metal powder raw material, it will Phosphoric acid presses 0.8~2.0 with absolute ethyl alcohol:100 ratio is mixed to prepare passivating solution, and passivating solution and the metal powder weighed is former Material is according to 0.4~0.6:1 ratio mixing after stirring 0.5~2h with mixer, is put into baking oven passivation, baking temperature for 40~ 42 DEG C, passivation time is 4~6h, obtains passivation powder.
Powder will be passivated with organic solution according to volume ratio 1:0.5~1 ratio mixing, 6~12h is stirred with mixer, Again with 5~15min of ultrasonic disperse, through screen filtration, the slurry for the even dispersion made after vacuum outgas, the viscosity of slurry for 40~ 80MPa.s。
Doctor-blade casting process is commonly called as scraper forming process, is a kind of important forming method for preparing large area film, is used The species such as organic solvent, dispersant, plasticizer, binding agent it is various, above-mentioned pulping process is a kind of feasible method, not Representative can only select this method.
(3) powder tape casting
During curtain coating environment temperature be 28~32 DEG C, will disperse slurry inject casting machine in, control casting machine speed be 0.1~ 0.5cm/s, the height of scraper is 1.2~2.4mm, and width is 100~300mm.
It is 30~40 DEG C to be cast biscuit drying temperature, and relative humidity is 30~60%, and the thickness of biscuit is after slurry drying 0.8~1.8mm carries out curing process in a nitrogen atmosphere, and solidification temperature is 120~200 DEG C, and hardening time is 1~5h, with stove It is cooled to room temperature.The dry curtain coating slab dense structure of preparation, porosity is low, surfacing, because containing more plasticizer, bonding The organic matters such as agent, density are 5.9~6.3g/cm3。
(4) degreasing, sintering
Curtain coating slab is placed on surface to be coated in the support plate of MgO micro mists, is placed into vacuum degreasing, sintering furnace, 2h~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 1080~1180 DEG C 2~4h of heat preservation sintering, sintered blank density are 6.0~6.5g/cm3。
Sintering temperature is too low, the connection and the diffusion of Si being unfavorable between Fe powder particles, and sintering temperature is excessively high then can be due to , there is coarse hole in the diffusion into the surface of Fe, Si element, is subsequently difficult to press, and rolling densification is difficult to realize.
During sintering can powder curtain coating 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 Do support plate (or burn boat), can also use the ceramic wafers such as corundum, zirconium oxide, but metallic plate thermal conductivity it is good and beneficial to uniformly burning Knot is shunk.
Uniformly tiny porous organization is formed after sintering.X-ray diffraction Discriminating materials are heterogeneous Fe (Si) phase, are had 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 one Si contents in kind Fe phases are low, have plastic deformation ability.
(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 1080~1180 DEG C, after multiple cold rolling-sintering, the thickness of plate reaches To 0.1~0.5mm, density reaches 7.33~7.43g/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%.
Since there are a large amount of holes and hard crisp phase, it is necessary to take and keep the temperature vacuum-sintering again at 1080 DEG C~1180 DEG C or go back 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 biscuit of 0.8~1.8mm, 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.
(6) high temperature sintering is homogenized
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 homogenization 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 reaches 7.34~7.44g/cm3。
Organic solution is with 10:1.0 methyl ethyl ketone and absolute ethyl alcohol is mixed solvent, using epoxy resin as bonding Agent, polyethylene glycol are plasticizer, and triethanolamine is dispersant, and the volume ratio of epoxy resin and polyethylene glycol presses 1:1, then by mixed Bonding solvent quality is 50~70%, and dispersant quality is 0.1%, and surplus is organic molten for the slurry that binding agent and plasticizer are formed Body.
With high-energy ball milling or rush rotation method obtain grain size≤3 μm simple substance Si powder.
Support plate described in step (4) burns boat using W, Mo, corundum or zirconia ceramics.
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 with the addition of a small amount of list in the reduction Fe powder of the big volumetric portion with good plasticity The fine Si powder of matter using organic curtain coating system, forms a kind of achievable powder and is cast molding composite material；Using being cast into Type prepares the uniform slab of density, Tissue distribution；By being not exclusively sintered, Fe powder particles is made to realize not exclusively and are connected, and Si Partially-alloyed, the high silicon steel blank of porous, with compressibility the incomplete alloying of formation is realized with Fe；Subsequently through more Passage cold rolling and sintering improve structural homogenity and compactness；Again by high-temperature diffusion process, the homogenization of Si is realized, so as to Obtain the high silicon steel band of high quality.This method realizes Technics Process Automation, continuous metaplasia by technique and equipment Design Production, can be mass-produced 0.1~0.5mm thickness, density >=7.34g/cm3High silicon steel band.
Description of the drawings
Fig. 1 is that the powder tape casting base of the embodiment of the present invention 2 is sintered the porous shape appearance figure of rear surface polishing；
Fig. 2 is XRD diffraction curve figures after the powder tape casting base of the embodiment of the present invention 2 is sintered；
Fig. 3 is XRD diffraction curve figures after powder tape casting-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 reduction 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 Fe- The mixed-powder of 6.7Si.Phosphoric acid and absolute ethyl alcohol are pressed 0.8:100 ratio is mixed to prepare passivating solution.By passivating solution with weighing Good metal powder raw material is according to 0.4:1 ratio mixing after stirring 0.5h with mixer, is put into baking oven passivation, baking temperature For 40 DEG C, passivation time 4h, passivation powder is obtained.
With 10:1.0 methyl ethyl ketone and absolute ethyl alcohol is mixed solvent, is increasing by binding agent, polyethylene glycol of epoxy resin Agent is moulded, triethanolamine is dispersant.The volume ratio of epoxy resin and polyethylene glycol presses 1:1, the addition of mixed solvent is 60%, the addition of dispersant is 0.1%, forms the organic solution of slurry.Powder will be passivated with organic solution according to volume ratio 1: 0.5 ratio mixing, 6h is stirred with mixer, then with ultrasonic disperse 5min, through screen filtration, made after vacuum outgas uniformly more Scattered slurry, the viscosity of slurry is 40MPa.s.
Environment temperature is 28 DEG C during curtain coating, and disperse slurry is injected in casting machine, controls casting machine speed as 0.5cm/s, The height of scraper is 2.4mm, and width is about 100mm.
It is 40 DEG C to be cast biscuit drying temperature, relative humidity 30%, and the thickness of biscuit is 1.8mm after slurry drying. Curing process is carried out under nitrogen atmosphere, solidification temperature is 200 DEG C, hardening time 5h, cools to room temperature with the furnace, and curtain coating slab is close It spends for 5.9g/cm3。
Curtain coating slab 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 1080 DEG C of heat preservation sintering 4h.It burns It is 6.0g/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 1080 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：1.8mm → 1.2mm → 0.92mm → 0.71mm → 0.50mm, i.e., after 4 cold rollings and 3 sintering, the thickness of plate reaches 0.50mm, density reach 7.33g/cm3。
For above-mentioned cold rolling made-up belt in 1350 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 reduction 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 Fe- The mixed-powder of 4.5Si.Phosphoric acid and absolute ethyl alcohol are pressed 2.0:100 ratio is mixed to prepare passivating solution.By passivating solution with weighing Good metal powder raw material is according to 0.6:1 ratio mixing after stirring 2h with mixer, is put into baking oven passivation, and baking temperature is 42 DEG C, passivation time 6h, obtain passivation powder.
With 10:1.0 methyl ethyl ketone and absolute ethyl alcohol is mixed solvent, is increasing by binding agent, polyethylene glycol of epoxy resin Agent is moulded, triethanolamine is dispersant.The volume ratio of epoxy resin and polyethylene glycol presses 1:1, the addition of mixed solvent is 60%, the addition of dispersant is 0.1%, forms the organic solution of slurry.Powder will be passivated with organic solution according to volume ratio 1:1 Ratio mixing, stir 12h with mixer, then with ultrasonic disperse 15min, through screen filtration, made after vacuum outgas uniformly more Scattered slurry, the viscosity of slurry is 80MPa.s.
Environment temperature is 32 DEG C during curtain coating, and disperse slurry is injected in casting machine, controls casting machine speed as 0.1cm/s, The height of scraper is 1.2mm, and width is about 300mm.
It is 30 DEG C to be cast biscuit drying temperature, relative humidity 60%, and the thickness of biscuit is 0.8mm after slurry drying. Curing process is carried out under nitrogen atmosphere, solidification temperature is 120 DEG C, hardening time 1h, cools to room temperature with the furnace, and curtain coating slab is close It spends for 6.3g/cm3。
Curtain coating slab 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 1180 DEG C of heat preservation sintering 2h.It burns It is 6.5g/cm to tie base density3.Sintered surface polishes porous pattern and sees Fig. 1, and material phase analysis XRD diffraction curves are shown in Fig. 2.
Uniformly tiny porous organization is formed after sintering, sees Fig. 1.X-ray diffraction Discriminating materials are heterogeneous Fe (Si) Phase, as seen in Figure 2, body-centred cubic several characteristic peaks have apparent separating phenomenon, illustrate that there are 2 kinds of different Fe of Si solid solubility Phase, wherein must have, the Si contents in a kind of Fe phases are low, have plastic deformation ability.
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 1180 DEG C of heat preservation sinterings.With 10 DEG C/min speed continuous warmings, soaking time is 1h.Specifically pressure-annealing schedule is：0.8mm → 0.63mm → 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 7.43g/cm3。
For above-mentioned cold rolling made-up belt in 1280 DEG C of vacuum-sintering 4h, it is about 0.10mm, density 7.44g/cm to obtain thickness3, Si Content is the 4.5% high silicon steel of single-phase homogeneous.
Embodiment 3
By the reduction 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 Fe- The mixed-powder of 6.5Si.Phosphoric acid and absolute ethyl alcohol are pressed 1.0:100 ratio is mixed to prepare passivating solution.By passivating solution with weighing Good metal powder raw material is according to 0.5:1 ratio mixing after stirring 1h with mixer, is put into baking oven passivation, and baking temperature is 40 DEG C, passivation time 5h, obtain passivation powder.
With 10:1.0 methyl ethyl ketone and absolute ethyl alcohol is mixed solvent, is increasing by binding agent, polyethylene glycol of epoxy resin Agent is moulded, triethanolamine is dispersant.The volume ratio of epoxy resin and polyethylene glycol presses 1:1, the addition of mixed solvent is 60%, the addition of dispersant is 0.1%, forms the organic solution of slurry.Powder will be passivated with organic solution according to volume ratio 1: 0.6 ratio mixing, 8h is stirred with mixer, then with ultrasonic disperse 7min, through screen filtration, made after vacuum outgas uniformly more Scattered slurry, the viscosity of slurry is 60MPa.s.
Environment temperature is 30 DEG C during curtain coating, and disperse slurry is injected in casting machine, controls casting machine speed as 0.3cm/s, The height of scraper is 1.4mm, and width is about 160mm.
It is 35 DEG C to be cast biscuit drying temperature, relative humidity 45%, and the thickness of biscuit is 1.2mm after slurry drying. Curing process is carried out under nitrogen atmosphere, solidification temperature is 160 DEG C, hardening time 3h, cools to room temperature with the furnace, and curtain coating slab is close It spends for 6.1g/cm3。
Curtain coating slab 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：1.2mm → 1.02mm → 0.72mm → 0.45mm → 0.27mm, i.e., after 4 cold rollings and 3 sintering, plate Thickness reach 0.27mm, density reaches 7.38g/cm3。
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 reduction 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 Fe- The mixed-powder of 5.8Si.Phosphoric acid and absolute ethyl alcohol are pressed 1.2:100 ratio is mixed to prepare passivating solution.By passivating solution with weighing Good metal powder raw material is according to 0.6:1 ratio mixing after stirring 1h with mixer, is put into baking oven passivation, and baking temperature is 42 DEG C, passivation time 6h, obtain passivation powder.
With 10:1.0 methyl ethyl ketone and absolute ethyl alcohol is mixed solvent, is increasing by binding agent, polyethylene glycol of epoxy resin Agent is moulded, triethanolamine is dispersant.The volume ratio of epoxy resin and polyethylene glycol presses 1:1, the addition of mixed solvent is 60%, the addition of dispersant is 0.1%, forms the organic solution of slurry.Powder will be passivated with organic solution according to volume ratio 1: 0.7 ratio mixing, stirs 9h, then with ultrasonic disperse 10min, through screen filtration, that is made after vacuum outgas is uniform with mixer The slurry of disperse, the viscosity of slurry is 55MPa.s.
Environment temperature is 30 DEG C during curtain coating, and disperse slurry is injected in casting machine, controls casting machine speed as 0.3cm/s, The height of scraper is 1.8mm, and width is about 200mm.
It is 30 DEG C to be cast biscuit drying temperature, relative humidity 50%, and the thickness of biscuit is 1.6mm after slurry drying. Curing process is carried out under nitrogen atmosphere, solidification temperature is 160 DEG C, hardening time 4h, cools to room temperature with the furnace, and curtain coating slab is close It spends for 6.0g/cm3。
Curtain coating slab 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 6.16g/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.1.6mm→ 1.23mm → 0.96mm → 0.72mm → 0.46mm → 0.32mm → 0.21mm, i.e., after 7 cold rollings and 6 sintering, plate Thickness reaches 0.21mm, and density reaches 7.41g/cm3。
For above-mentioned cold rolling made-up belt in 1320 DEG C of vacuum-sintering 2h, it is about 0.22mm, density 7.42g/cm to obtain thickness3, Si Content is 5.8%, and the XRD analysis figure of final plate is shown in Fig. 3, is the high silicon steel of single-phase homogeneous.

Claims (6)

1. a kind of method that powder tape casting prepares single-phase Fe-6.5%Si silicon steel, it is characterised in that comprise the following steps：
(1) raw material powder prepares
Using -100 mesh reduced iron powders, Fe >=98.5% in reduced iron powder, remaining is Si, Mn, P, S and other are inevitably miscellaneous Matter, 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 ingredients, passivation, slurry prepare
According to the ratio of Fe-4.5~6.7%Si, reduction Fe powder and Si powder are weighed, metal powder raw material is formed, by phosphoric acid and nothing Water-ethanol presses 0.8~2.0:100 ratio is mixed to prepare passivating solution, by passivating solution and the metal powder raw material weighed according to matter Amount is than being 0.4~0.6:1 ratio mixing after stirring 0.5~2h, is put into baking oven passivation, and baking temperature is 40~42 DEG C, passivation Time is 4~6h, obtains passivation powder；
Using organic curtain coating system, by passivation powder with organic solution according to volume ratio 1:0.5~1 ratio mixing, with stirring Machine stirs 6~12h, then with 5~15min of ultrasonic disperse, through screen filtration, the slurry for the even dispersion made after vacuum outgas, slurry The viscosity of material is 40~80MPa.s；
(3) powder tape casting
During curtain coating environment temperature be 28~32 DEG C, will disperse slurry inject casting machine in, control casting machine speed be 0.1~ 0.5cm/s, the height of scraper is 1.2~2.4mm, and width is 100~300mm；
It is 30~40 DEG C to be cast biscuit drying temperature, and relative humidity is 30~60%, after slurry drying the thickness of biscuit for 0.8~ 1.8mm, carries out curing process in a nitrogen atmosphere, and solidification temperature is 120~200 DEG C, and hardening time is 1~5h, furnace cooling To room temperature, the dry curtain coating slab density of preparation is 5.9~6.3g/cm3；
(4) degreasing, sintering
Curtain coating slab 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 1080~1180 DEG C of guarantors Temperature 2~4h of sintering, sintered blank density are 6.0~6.5g/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 1080~1180 DEG C, after multiple cold rolling-sintering, the thickness of plate reaches 0.1~0.5mm, density reach 7.33~7.43g/cm3；
(6) high temperature sintering is homogenized
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 homogenization of existing Si forms single-phase alloy, obtains the high silicon steel of homogeneous, and the thickness of plate is almost unchanged after densification sintering, is 0.1 ~0.5mm, density reach 7.34~7.44g/cm3。
2. the method that a kind of powder tape casting as described in claim 1 prepares single-phase Fe-6.5%Si silicon steel, feature exist In：Organic solution described in step (2) is with 10:1.0 methyl ethyl ketone and absolute ethyl alcohol is mixed solvent, is viscous using epoxy resin Agent is tied, polyethylene glycol is plasticizer, and triethanolamine is dispersant, and the volume ratio of epoxy resin and polyethylene glycol presses 1:1, then press Mixed solvent quality is 50~70%, and dispersant quality is 0.1%, and surplus is organic molten for the slurry that binding agent and plasticizer are formed Body.
3. the method that a kind of powder tape casting as described in claim 1 prepares single-phase Fe-6.5%Si silicon steel, feature exist In：With high-energy ball milling or rush rotation method obtain grain size≤3 μm simple substance Si powder.
4. the method that powder tape casting as described in claim 1 prepares single-phase Fe-6.5%Si silicon steel, it is characterised in that：Step Suddenly (5) are sintered, by 5~10 DEG C/min when re-sintering for 1080 DEG C~1180 DEG C under vacuum-sintering or restitutive protection's atmosphere Continuous warming, during thickness of slab >=1mm, soaking time is 1~2h；Thickness of slab is in 0.1~1mm, and soaking time is reduced to 0.5~1h, often After secondary sintered accumulation drafts reaches 30~45%, it is sintered 1 time again, 0.1 is rolled down to from the biscuit of 0.8~1.8mm~ 0.5mm, it is necessary to be sintered 4~8 times again.
5. the method that powder tape casting as described in claim 1 prepares single-phase Fe-6.5%Si silicon steel, it is characterised in that：It is high Overlapping places sintering plate during temperature sintering, and interlayer is laid with MgO powder.
6. the method that powder tape casting as described in claim 1 prepares single-phase Fe-6.5%Si silicon steel, it is characterised in that：Step Suddenly the support plate described in (4) burns boat using W, Mo, corundum or zirconia ceramics.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113771274A (en) * 2021-11-10 2021-12-10 成都佳驰电子科技股份有限公司 Low-cost magnetic wave-absorbing waterproof gasket preparation device and method

Citations (6)

* 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
CN104036906A (en) * 2014-06-05 2014-09-10 浙江大学 Tape-casting temperature isostatic pressing composite molding preparation method of metal soft magnetic composite material
CN104073660A (en) * 2014-06-05 2014-10-01 浙江大学 Method for preparing metal soft magnetic compound material by tape casting
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 (6)

* 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
CN104036906A (en) * 2014-06-05 2014-09-10 浙江大学 Tape-casting temperature isostatic pressing composite molding preparation method of metal soft magnetic composite material
CN104073660A (en) * 2014-06-05 2014-10-01 浙江大学 Method for preparing metal soft magnetic compound material by tape casting
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》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113771274A (en) * 2021-11-10 2021-12-10 成都佳驰电子科技股份有限公司 Low-cost magnetic wave-absorbing waterproof gasket preparation device and method
CN113771274B (en) * 2021-11-10 2022-03-08 成都佳驰电子科技股份有限公司 Low-cost magnetic wave-absorbing waterproof gasket preparation device and method

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