CN102489677A - Block-type amorphous alloy plate continuous casting device and method thereof - Google Patents
Block-type amorphous alloy plate continuous casting device and method thereof Download PDFInfo
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- CN102489677A CN102489677A CN2011104420198A CN201110442019A CN102489677A CN 102489677 A CN102489677 A CN 102489677A CN 2011104420198 A CN2011104420198 A CN 2011104420198A CN 201110442019 A CN201110442019 A CN 201110442019A CN 102489677 A CN102489677 A CN 102489677A
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Abstract
The invention discloses a block-type amorphous alloy plate continuous casting device and a method thereof, and belongs to the technical field of preparation of metal materials. The device and the method are characterized by combining the characteristics of block-type amorphous alloy plate continuous casting cooling roller cooling and mold cooling; solidification and molding of an alloy are finished between two parallel cooling bands which move synchronously; a smelted female alloy is melted and subjected to heat preservation in a crucible, and is poured between the two parallel cooling bands cooled by water through a flowing nozzle with a rectangular section under set temperature to be cooled and solidified, so that an amorphous plate is formed; and the cooling bands drive the solidified amorphous plate to move at certain speed under the action of a driving roller and a positioning roller and finish a continuous casting process. The device is simple in structure and high in cooling speed; and the solidification and the throwing of metal are finished in the cooling bands, so that the process stability is high, and the size of the cast ingot is convenient to adjust. According to the device and the method, thick block-type amorphous alloy plates can be prepared efficiently and continuously.
Description
Technical field
The invention belongs to technical field of metal material preparation, specially refer to the continuous technology of preparing of non-crystaline amorphous metal and nonequilibrium freezing material sheet material.
Background technology
Non-crystaline amorphous metal is also claimed glassy metal, is to have one type of solid material that unique atom is formed structure, had metal and glass performance concurrently.The composed atom of non-crystaline amorphous metal is long-range unordered, short-range order arrangement; There are not crystal defects such as crystal boundary, dislocation, fault in its inside; Physics, chemistry and mechanical property keep isotropism; Be in metastable state on the thermodynamics, more than crystallization temperature, the crystalline structure phase transformation will take place, but below crystallization temperature, can steady in a long-termly exist.Block amorphous alloy then has high heat endurance and big glass forming ability; Even alloy melt also can form amorphous phase under the slow cooling velocity of 0.1～hundreds of K/s, can obtain three-dimensional dimension with the method for permanent mold casting and reach the above single-phase block materials of amorphous of millimeter level.
Compare with traditional metal material, block amorphous alloy has excellent performances such as mechanics, physics and chemistry.Like the high strength that is difficult in the crystal alloy obtain and high specific strength, big elastic limit, low elastic modulus, excellent corrosion-resistant, abrasion resistance properties and good soft magnetic characteristic etc.Block amorphous alloy has the wide supercooling liquid phase region before tangible glass transformation temperature and the crystallization; When temperature is between supercooling liquid phase region; Because the variation of structural relaxation and free volume; Be similar to the ruckbildung of oxide glass, viscosity sharply reduces, shows the VISCOUS FLOW characteristic, can carry out high accuracy superplastic deformation and nearly clean shape processing.Therefore, block amorphous alloy is with a wide range of applications in Aero-Space, micro electronmechanical, national defense industry, information technology, the fields such as body material and sports goods of giving birth to.
Common non-crystaline amorphous metal, the formation of amorphous phase needs 10
6The cooling velocity that K/s is above, so big cooling velocity makes non-crystaline amorphous metal can only process low-dimensional materials such as strip, filament and powder, and effective thickness is below 100 μ m.1988, people such as Inoue found subcooled liquid stabilisation phenomenon in multicomponent alloy system, and these alloys have wide supercooling liquid phase region and big glass forming ability, can obtain the single-phase block materials of amorphous with copper mold casting method.After this; The researcher has in development of new and has carried out a large amount of work aspect the alloying component of large-amorphous forming capacity; In numerous alloy systems, prepare block amorphous alloy; Wherein amorphous forms nearly 20 of the alloy system that critical dimension reaches Centimeter Level, and the amorphous of alloys such as Zr is basic, Pd is basic, Cu is basic, Mg is basic, Ni is basic, La base forms size above 2 centimetres, and critical cooling rate is less than 5K/s.Exploitation with block amorphous alloy of large-amorphous forming capacity; Not only make block amorphous alloy become possibility, also for adopting some high efficiency, the block amorphous alloys of the next preparation in a large number of ordinary metallic material forming technique cheaply that feasible precondition is provided as the new high-tech material large-scale industrial application.
The method for preparing block amorphous alloy; Comprise melt water quenching, copper mold casting method, arc-melting casting, high pressure casting, microcast process and powder curing method etc.; It all is the non-continuous process of single-piece or small lot; Production efficiency is low, cost is high, has limited the heavy industrialization of block amorphous alloy and has used.Block amorphous alloy sheet material can be used for high performance structural and building blocks of function, also is convenient to utilize methods such as hot pressing, hot extrusion, hot rolling and blowing to make various accurate devices.The non-crystaline amorphous metal strip, the especially thickness that utilize continuously shaped technology to prepare infinite in length system in a large number surpass millimetre-sized block amorphous alloy sheet material, are the targets that the researcher constantly pursues always.
Single roller melt supercooled method is called for short single-roller method, has big cooling velocity, can reach 10
6K/s through changing the structure of nozzle and chill roll, has realized the preparation of wide cut amorphous thin ribbon, and width can reach hundreds of millimeters.But molten metal flow speed mainly is to be controlled by the aperture of nozzle, inside and outside pressure differential and the VISCOUS FLOW of solidifying between the front end in the single-roller method; Guarantee that in order to obtain enough cooling velocities motlten metal is frozen into amorphous state; Generally more than 30m/s, the thickness that big velocity of rotation has limited amorphous ribbon is below 20 μ m for the velocity of rotation on chill roll surface.Reduce the rotating speed of chill roll, can improve the thickness of amorphous band,, use single-roller method can obtain the be altogether unjustifiable crystal zone of thickness, but the chill roll low-speed running is unfavorable for forming stable molten bath and continuous cooling process as 50-75 μ m for the big alloy of amorphous formation ability.At present, with the thickness of the block amorphous alloy band of single-roller method preparation less than 100 μ m.
Two roller melt supercooled methods are called for short double roller therapy, also are one of important method of preparation amorphous thin ribbon, have developed the multiple continuous method for preparing block amorphous alloy sheet material based on double roller therapy.Patent CN 1486800A discloses a kind of bulk amorphous alloys continuous casting rolling technology, and melted alloy in crucible is injected into molten metal in two counterrotating water-cooled rolls then, adopts the roll casting to prepare bulk amorphous alloy sheet material, bar and special-shaped section bar.U.S. Pat 2006/0260782A1 discloses a kind of continuous casting apparatus and method of block amorphous alloy sheet material; Device adopts the counterrotating chill roll of many groups; The slab thickness of preparation is 0.1～10mm; Casting speed is 0.5～10cm/s, but cooling velocity only limits to have the Zr bast block metal glass moulding that contains Be of big glass forming ability less than 10 ℃/s.Theoretically, double roller therapy carries out two-sided cooling to metal bath, and cooling capacity is greater than single-roller method, but owing to the EFFECTIVE RANGE of metal bath in the double roller therapy and chill roll is short, it is much little that actual cooling velocity is wanted; Casting and roll process has improved the contact distance of metal bath with roll, but solidified layer thickness and technology stability that control contacts with roll are that a difficult problem to be solved is arranged always.
According to the characteristics of solidifying of block amorphous alloy, a kind of graphite/water cooled copper mould combined type casting mold (ZL200920013438.8) has been invented by this seminar, and composite mould has big cooling velocity and the big thermograde of solidification front.Utilize graphite/water cooled copper mould combined type casting mold to develop the apparatus and method (ZL 200910011405.4) of block metal glass horizontal continuous-casting; Device comprises two independently vacuum chambers; Utilize the draught head assistant alloy moulding between vacuum chamber, can realize excellent wire rod, square billet, sheet material, tubing and special-shaped material etc. continuously shaped of different cross section size.The cooling of alloy mainly relies on water cooled copper mould, and the strand that solidifies is by constantly output of motor-driven draw bar pulling.
For the continuously shaped process of block amorphous alloy, the big cooling velocity of device is necessary and useful, and cooling velocity is big more, and it is big more that the amorphous of ingot casting forms size.The present invention has combined the characteristics of block amorphous alloy continuous casting plate, the cooling of band chill roll and casting mold cooling, and its principle, structure and method are not seen public reported as yet.
Principle of the present invention is:
1. metal bath cools off, solidifies on two salbands (or crystallizer), and cooling capacity is strong.Metal bath contacts cooling rapidly with the salband surface after stem bar gets into salband (or crystallizer), salband has good heat conduction and heat storage capacity, makes alloy melt obtain big cooling velocity; Molded alloy is cooled before leaving salband always, and the time of contact of alloy and salband is long, can derive by efficiently that sheet material is inner heat, and cooling capacity is strong, especially is fit to the cooling of big thickness sheet material.
2. do not have relative motion between alloy and the salband, solidification shrinkage is little during alloy generation amorphous phase-change, and the interface resistance between alloy and the salband is little, can obtain big cooling velocity.
3. salband cools off with medium, and the heat that sheet material solidifies release continues to derive through salband, realizes cooling continuously.
4. the alloy strap clamp that is cooled is held and is moved with certain speed along casting direction; Salband not only makes the alloy melt cooling, solidifies; Also drive the sheet material motion of solidifying, the effect of playing throwing; The simple structure of device, it is little to have solved the non-crystaline amorphous metal solidification shrinkage simultaneously, the problem of in crystallizer, " freezing " easily.
5. the alloy that gets into salband cools off, moves with salband when solidifying; The salband front end constantly pours into the alloy of fusion; Can continuously pull out the strand of section configuration, size constancy from the other end of salband; Realize the continuous casting process, obtain arbitrarily or the foundry goods of length-specific.
Summary of the invention
The invention provides a kind of block amorphous alloy plate, band continuous casting apparatus and method.
Technical scheme of the present invention is following:
A kind of block amorphous alloy plate, band continuous casting apparatus comprise crucible, thermocouple, stem bar, salband or crystallizer, driven roller, registration roller, dummy bar head, buncher and cutting machine, in crucible, melt foundry alloy, adjustment pouring temperature and pressure; Molten metal is poured into cooling between the salband, solidifies through the stem bar and the crystallizer of square-section, forms non-crystaline amorphous metal plate, band; Buncher drives driven roller and rotates, and salband and the amorphous plate that solidifies, band are synchronized with the movement with certain speed, and registration roller keeps salband to be parallel to each other, the inner water flowing cooling of salband; After plate, band reach and need length, cut off, obtain block amorphous alloy continuous casting plate, band through cutting machine.
Salband is used the heat conductive metal material, and like stainless steel, aluminium alloy, copper alloy etc., better suited material has chromium-copper, beryllium copper, dispersion strengthening copper alloy, oxygenless copper alloy; The inner water flowing cooling of salband, outer surface polishes or chromium plating is handled; The gap of salband is 0.05～10cm, and the contact length of salband and plate, band is 5～500cm.
Be provided with driven roller and registration roller in the salband, driven roller keeps rotating synchronously, and salband is moved along casting direction, and the movement velocity of salband is 0.01～50m/min; At least one group of registration roller keeps salband to be parallel to each other.
Crucible and stem bar are with not making with the exotic material of block amorphous alloy generation chemical reaction, like high purity graphite; Crucible is with eddy-current heating or resistance heated, and serviceability temperature is greater than 500 ℃; Crucible is placed in the vacuum environment or with gas and flux protection; The outlet of stem bar can be rectangle or other abnormal shapes, and when adopting rectangle, width is 0.05～100cm, and length is greater than 0.1cm.
Device can adopt level or continuous vertical casting mode, and the height of claimed apparatus is greater than the length of desired blocks non-crystaline amorphous metal continuous casting sheet material during continuous vertical casting.
Use the method for above-mentioned block amorphous alloy sheet material continuous casting apparatus, may further comprise the steps:
A, alloy melting and insulation: dummy bar head is put into sealing between stem bar, dummy bar head and stem bar (or crystallizer); Melted foundry alloy is put into crucible, and the Fast Heating crucible makes the foundry alloy fusing, and through thermocouple measurement metal bath temperature, the temperature of control metal bath is higher than alloy liquid phase line temperature more than 5 ℃, insulation a period of time, makes the metal bath temperature even; Under vacuum, during melted alloy, before beginning to heat, crucible is evacuated to required vacuum;
B, alloy melt cast: the temperature of adjustment metal bath is higher than 5～200 ℃ of alloy liquid phase line temperature, and the pulling dummy bar head breaks away from it gradually in stem bar, and metal bath is flowing between the salband through stem bar and crystallizer under static pressure or the gas pressure effect;
C, continuous casting: start buncher, driven roller is rotated, drive salband and move with certain speed along casting direction, stationary roll makes salband keep being parallel to each other; The metal bath that gets into salband cools off, solidifies formation non-crystaline amorphous metal plate, band when moving together with salband; When reaching Len req, start cutting machine and cut off non-crystaline amorphous metal plate, band, accomplish the continuous casting process.
The present invention has adopted technique scheme, has the following advantages and good effect: 1. the time of contact of salband and contour alloy long, cooling capacity is big, is fit to the moulding of block amorphous alloy plate, band; 2. do not have relative motion between salband and the contour alloy, the thermal resistance at interface is little, and ingot casting has big cooling velocity; 3. solidifying with output of alloy accomplished in salband, and apparatus structure is simple; 4. alloy melt moves along casting direction when in salband, cooling off, solidifying, and forms the continuous casting process, obtains non-crystaline amorphous metal continuous casting plate, band.
Description of drawings
Accompanying drawing is a block amorphous alloy sheet material continuous casting theory structure sketch map of the present invention.
Among the figure: 1 crucible, 2 thermocouples, 3 stem bars, 4 crystallizers, 5 salbands, 6 driven rollers, 7 registration rollers, 8 dummy bar heads,
9 bunchers, 10 cutting machines.
The specific embodiment
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is further described.
Block amorphous alloy sheet material continuous casting apparatus and the method for utilizing the present invention to propose, preparation thickness are that 10mm, width are the Cu-Zr base block amorphous alloy continuous casting sheet material of 50mm.
A, alloy melting and insulation: the selection nominal composition is Cu
36Zr
48Al
8Ag
8Block amorphous alloy is pressed atomic ratio configuration alloy raw material, and melting obtains foundry alloy under vacuum arc furnace ignition, and the liquidus temperature that uses DTA to record alloy is 870 ℃, and the rate of heat addition during test is 20K/min; Crucible 1, stem bar 3 and crystallizer 4 adopt high purity graphites to make, and place in the vacuum chamber, stem bar sectional dimension be 10 * 50mm
2, wall thickness 15mm puts into dummy bar head 8 between stem bar, dummy bar head and stem bar and to seal; Foundry alloy is put into crucible, be evacuated to 10
-3Pa, Fast Heating crucible make the foundry alloy fusing, and the temperature of measuring, control metal bath through thermocouple 2 is 920 ℃, and insulation 30min makes the alloy melt temperature even;
B, alloy melt cast: the temperature of alloy melt is 970 ℃ in the adjustment crucible 1; Cooling water flow in the salband 5 is 5L/min; The inside and outside pressure differential of vacuum chamber is 0.2Mpa; Pulling dummy bar head 8 breaks away from it gradually in stem bar 3, metal bath is flowing between the salband through stem bar and crystallizer under static pressure and the gas pressure effect;
C, continuous casting: start buncher 9, driven roller 6 is rotated, drive salband along the speeds of casting direction with 20cm/min, stationary roll 7 makes salband keep being parallel to each other; The alloy melt that gets into salband cools off, solidifies formation sheet material when being synchronized with the movement with salband; After cutting machine 10 cut off, acquisition length reached and is that 500mm, cross section are 10 * 50mm
2Continuous casting sheet material; The observation by light microscope microscopic structure after sample section polished, polishes, corrodes, is used in the two ends of intercepting sheet material and middle part, measures the phase structure of sample with X-ray diffractometer.The microscopic structure of sample is even, does not find to have the different phase structures of light and shade deviation; X-ray diffraction spectrum is the big and wide slow wave peak that typical non-crystaline amorphous metal has, and does not have the sharp-pointed diffraction maximum of tangible corresponding crystal structure, and sheet material has the amorphous phase structure.
Claims (7)
1. a block amorphous alloy sheet material continuous casting apparatus comprises crucible (1), thermocouple (2); Stem bar (3), crystallizer (4), salband (5); Driven roller (6), registration roller (7), dummy bar head (8); Buncher (9) is characterized in that: crucible (1) and stem bar (3) with not with the high temperature resistant nonmetallic materials of block amorphous alloy generation chemical reaction; Crucible is with eddy-current heating or resistance heated, and serviceability temperature is greater than 500 ℃; Salband (5) is used the heat conductive metal material; Inner water flowing of salband or the cooling of other medium, outer surface polishes or chromium plating is handled; The gap of salband is 0.05～10cm, and the contact length of salband and forming metal is 5～500cm; Be provided with driven roller (6) and registration roller (7) in the salband, buncher (9) drives driven roller and rotates synchronously, makes the outer salband motion of driven roller; At least one group of registration roller keeps salband to be parallel to each other.
2. block amorphous alloy sheet material continuous casting apparatus according to claim 1 is characterized in that the cross section of stem bar and crystallizer (4) is a rectangle, and width is 0.05～10cm, and length is greater than 0.1cm.
3. block amorphous alloy sheet material continuous casting apparatus according to claim 1 is characterized in that, crucible (1) and stem bar (3) adopt high purity graphite.
4. block amorphous alloy sheet material continuous casting apparatus according to claim 1 is characterized in that, salband adopts stainless steel, aluminium alloy, copper alloy.
5. block amorphous alloy sheet material continuous casting apparatus according to claim 3 is characterized in that, salband adopts chromium-copper, beryllium copper, dispersion strengthening copper alloy, oxygenless copper alloy.
6. use the method for claim 1,2,3,4 or 5 said block amorphous alloy sheet material continuous casting apparatus, its characteristic may further comprise the steps:
A, alloy melting and insulation: dummy bar head (8) put between stem bar (3), dummy bar head and stem bar seal; Melted foundry alloy is put into crucible (1), and the Fast Heating crucible makes the foundry alloy fusing, measures the metal bath temperature through thermocouple (2), and the temperature of control metal bath is higher than alloy liquid phase line temperature more than 5 ℃, and insulation makes the metal bath temperature even; Under vacuum, during melted alloy, before beginning to heat, crucible is evacuated to required vacuum;
B, alloy melt cast: the temperature of adjustment metal bath is higher than 5～200 ℃ of alloy liquid phase line temperature; Pulling dummy bar head (8) breaks away from it gradually in stem bar (3), metal bath is getting between crystallizer (4) and the salband (5) through stem bar under static pressure or the gas pressure effect; When crystallizer was made with nonmetallic materials, alloy melt cooled off in salband, solidifies; When crystallizer was made with metal material, alloy melt is moulding in crystallizer, in salband, cooled off;
C, continuous casting: start buncher (9), driven roller (6) is rotated synchronously, drive salband and move along casting direction with the speed of 0.01～50m/min, stationary roll (7) makes salband keep being parallel to each other; The alloy that gets into salband is cooled and cools off, solidifies formation block amorphous alloy sheet material when strap clamp is held motion; When sheet material reaches Len req, start cutting machine (10), cut off sheet material, accomplish the continuous casting process.
7. a kind of block amorphous alloy sheet material continuous casting apparatus according to claim 6; It is characterized in that: employing level or continuous vertical casting mode, the height of claimed apparatus is greater than the length of desired blocks non-crystaline amorphous metal continuous casting sheet material during continuous vertical casting.
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Cited By (4)
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| CN103008582A (en) * | 2012-12-18 | 2013-04-03 | 广东工业大学 | Continuous casting device and method for copper pipe with straight fins at inner wall |
| WO2018082240A1 (en) * | 2016-11-01 | 2018-05-11 | 东莞市逸昊金属材料科技有限公司 | Continuous casting system for amorphous master alloy ingot and usage method therefor |
| CN109957732A (en) * | 2019-04-08 | 2019-07-02 | 东北大学 | A kind of method that zirconium-base amorphous thin strip is continuously prepared |
| CN114799096A (en) * | 2022-05-17 | 2022-07-29 | 张秀英 | Horizontal continuous casting furnace and rapid furnace starting method |
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Application publication date: 20120613 |