CN102660715B - Continuous preparation equipment and process for fiber-reinforced metal glass composite filament - Google Patents
Continuous preparation equipment and process for fiber-reinforced metal glass composite filament Download PDFInfo
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- CN102660715B CN102660715B CN201210168417.XA CN201210168417A CN102660715B CN 102660715 B CN102660715 B CN 102660715B CN 201210168417 A CN201210168417 A CN 201210168417A CN 102660715 B CN102660715 B CN 102660715B
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Abstract
The invention provides continuous preparation equipment and a process for a fiber-reinforced metal glass composite filament, and belongs to the field of amorphous alloy (metallic glass). The continuous preparation equipment is composed of a vacuum system, a pay-off wheel set, a heating system, a cooling device and a dragging mechanism. A heating carrier is placed in the high vacuum system so as to obtain a composite interface with good bonding property, no blends and complete cleaning performance. By adopting the method for paying off, a double-guide-wheel device is used, the two guide wheels are tangent in the two guide wheels, and the lower guide wheel is connected with a motor so as to directly wind the prepared filament, thus realizing the continuous and large-scale production and achieving the purposes of short procedures and energy conservation and consumption reduction. The continuous preparation equipment and process are applied to preparation of armour piercing materials and other uses.
Description
Technical field
The invention belongs to non-crystaline amorphous metal field, particularly the continuous production equipment and technology of a kind of fiber-reinforced metal glass composite material silk.
Background technology
Metallic glass (claiming again non-crystaline amorphous metal) refers in solid-state lower atomic arrangement to have short range order and long-range is unordered, and in certain temperature range, keeps the metastable metal alloy of this state.In recent ten years, the development of block metal glass is a milestone of its evolution especially, makes metallic glass become possibility as structured material.
Compare with conventional crystal material, block metal glass has higher intensity (～2GPa), large elastic limit (2%～3%) and the good outstanding advantages such as erosion resistance.Just because of its special performance, make block metal glass in fields such as sports goods, electronics, medical science and national defence, obtained more and more widely application (document 1, Mark Telford, Materials Today, Vol.3,2004, PP36).
Yet metallic glass did not almost have plastix strain to produce when room temperature carrying is lost efficacy, and showed as typical brittle rupture mode, thereby had seriously limited its application as engineering materials.Around the improvement of block metal glass temperature-room type plasticity, carried out research widely both at home and abroad.Research in recent years finds, thereby introduce the distribution that second-phase can change shear zone in block metal glass tissue, increases its temperature-room type plasticity, the good novel material of acquisition comprehensive mechanical property.This second-phase can be additional, can be also interior life (document 2, H. Choi-Yim, R. D. Conner, F. Szuecs and W. L. Johnson, Acta Materialia, Vol 50,2002, PP2737).Wherein, tungsten filament strengthens zirconium-based metallic glass composite material and receives much concern because of its unique performance.Zr bast block metal glass is under tensile stress or action of compressive stress, the shear fracture that can have shearing force to cause, surface of fracture is in the plane of action of maximum shear stress, there is good self-sharpening, after strengthening with tungsten filament, improve intensity and density, reached the particular requirement of high-density, self-sharpening, can be used as armour-piercing material.By rational interface and volume fraction, control, in this class matrix material of having prepared at present, maximum compression breaking tenacity is up to 2600MPa, plasticity reaches 13.5%(document 3, M.L. Wang, G.L. Chen, X. Hui, Y. Zhang and Z.Y. Bai, Intermetallics, in press).The main method of preparing at present tungsten filament enhancing bulk metal glass composite material is infiltration casting (document 4, Wang Meiling, Hui Xidong, Dong Wei, Liu Xiongjun, Chen Guoliang. interface of W fiber reinforced ZrTiCuNiBeNb bulk metallic glass matrix composite. China YouSe Acta Metallurgica Sinica, Vol.14, 2004, P1632, document 5, Zhang Xingchao, Chen Xiaohua, to open brave. the tungsten filament of superstrength and plasticity strengthens ZrTiCuNiBeNb metal glass composite material Rare Metals Materials and engineering, 2008, 37(supplementary issue 4): 786-789), yet a shortcoming of infiltration casting maximum is that fiber and aluminium alloy are long duration of contact, therefore, between fiber and melt or between fiber and the high temperature matrix that solidifies, there is surface reaction, reinforcement role reduces.
Summary of the invention
The object of the invention is to develop a kind of short flow process, be suitable for large-scale commercial production, and can obtain the fiber-reinforced metal glass based composite material silk continuous production equipment and technology of relatively clean compound interface.
A continuous production equipment for fiber-reinforced metal glass composite material silk, as shown in Figure 1.By vacuum system (9), pre-heating system (3), heating system (5), cooling system (6), haulage gear, formed, it is characterized in that haulage gear top is provided with unwrapping wire wheels (1), unwrapping wire wheels lower end is also provided with two unwrapping wire guide wheels (2), cooling system bottom is provided with a take-up guide wheel (7), unwrapping wire and take-up two guide wheel vertical directions are tangent, and bottom guide wheel is connected with motor, the silk of preparation directly can be wound up, realize continuously and producing; Cooling system (6) is tightly placed in crucible (4) bottom, guarantees that coated aluminium alloy rapid solidification forms metallic glass.
A production technique that adopts the continuous production equipment of above-mentioned fiber-reinforced metal glass composite material silk, is characterized in that:
(1) alloy preparing according to nominal composition is first smelted into uniform mother alloy with electric arc furnace, then mother alloy and wire is contained in to bottom and is with in foraminate crucible.
(2) metallic glass alloys liquid applies single metal wire: single metal wire one end from-inner-to-outer is through the aperture of crucible, remelting mother alloy insulation in process furnace, then by haulage gear by the drop-down wire being immersed in melt of driven by motor, make its surface uniform dipping layer of metal glassy alloy liquid, cooling through aluminium alloy behind heating zone.
(3) many one metal wires of metallic glass seepage flow process: the wire after primary coating is through actinobacillus wheel composition bundle or directly through an actinobacillus wheel bunchy, wire bundle one end from-inner-to-outer is through the aperture of crucible, remelting mother alloy insulation in process furnace, then by haulage gear by the drop-down wire bundle being immersed in melt of driven by motor, make its even Maceration alloy liquid, after passing heating zone, pass through the quick cooling formation metallic glass matrix of heat-eliminating medium.
(4) the final metal glass clad metal wire composite material with higher-strength and certain stretch percentage elongation that obtains.
Wire is selected tungsten filament, and metallic glass alloys is selected zirconium base alloy.Diameter wiry selects a micron level diameter from micron level diameter to hundreds of all can.
Motor traction wire drawing speed is 1-3m/min, and the type of cooling of refrigerating unit is gas cold trap, heat of liquid conduction or solid thermal conduction+gas cold trap hybrid mode.
In this preparation method, heating carrier is placed in high vacuum system, can obtain in conjunction with intact, nothing and be mingled with completely clean compound interface, after present method unwrapping wire, adopt upper and lower two guide wheel device, two guide wheel vertical directions are tangent, and bottom guide wheel is connected with motor, the silk of preparation directly can be wound up, realize continuous large-scale and produce, reach short flow process, energy-saving and cost-reducing object.
We in the past for the patent of " a kind of continuous production equipment and technology of metal glass clad metal wire composite material " obtain the authorization (patent No. is: ZL200710120355.4), now the patent of application is different from granted patent the following aspects:
1. processing step is different.Moulding process for once in the past: single metal wire applies non-crystaline amorphous metal liquid and produces effect very much, if preparation fiber-reinforced metal glass composite material, utilize granted patent can only directly once infiltrate with regard to moulding by wire bundle, so, aluminium alloy is difficult to go deep into wire bundle inside in the short period of time, is full of hole between wire, in order to solve the problem of infiltration completely, can only extend the infiltration time, but such consequence is aluminium alloy, react violent with wire.In order to overcome the infiltration problem of the wire bundle of patent in the past, newly apply for a patent technique two steps (as above shown in process description) that are divided into as implied above, it should be noted that metallic glass alloys liquid applies the object of single metal wire, on the one hand when making second step technique interalloy liquid seepage flow wire bundle, reduce aluminium alloy and with the wetting angle between the wire of coat, reduce and infiltrate resistance, thereby make wire bundle inside easily soak full non-crystaline amorphous metal liquid.On the other hand, reduce the infiltration time, reduce aluminium alloy and reaction times wiry.
2. the difference of processing step, has determined the new design of the unwrapping wire wheels of Preparation equipment.For preparing metallic glass, apply multiple wire, must overcome the interference of multifibres course each other, once multifibres can not be advanced according to the route of arranging in advance, between silk and silk, twine and be connected together so, cause test failure.For this problem, consider again space constraint, by the arrangement design of a plurality of wire wheels, be form shown in Fig. 2.Unwrapping wire wheels comprise at least 6 actinobacillus wheels (can also increase as required), single metal wire can be placed on respectively on single actinobacillus wheel, after guide wheel by each wire wheel, then each root monofilament is concentrated bunchy on the guide roller on top, in preparation process, just can solve like this between each one metal wire and be wound around and knotting problem, the product cross section of preparation just can be more even, each actinobacillus wheel is loaded with the actinobacillus wheel of individual thread simultaneously, the product length that like this prepared by single just can be elongated, thereby can increase productivity.
3. put the tension control of a system
The finished product wire that wire wheel basic size and business are sold is coiled quite, can determine that on the one hand the phenomenons such as cracking or clot do not occur wire on such circumferential curvature.In addition on the one hand also for streamlined operation provides convenience.
No matter be the wires such as tungsten filament or Stainless Steel Wire, the phenomenons such as due to self elasticity, easy appearance is loosening, slippage.If in the situation of mariages or multifibres, may there is the phenomenon of spooling.For above-mentioned phenomenon, designed the tension control system of putting silk in continuous manufacturing processed, as shown in Figure 3.By the movement of screw rod, regulate the size of the power of tensioning spring, thereby control the frictional force of wire wheel motion, adjustment of tonicity size.
4. the design of solid thermal conduction cooling system
By solid thermal, conduct to realize cooling principle as shown in Figure 4.Cooling hole by four separately independently mobilizable cooling copper wall form, movable slider connects cooling copper wall and spring.No matter material diameter becomes large or diminishes, can by spring move freely guarantee that matrix material and cooling copper wall are permanently connected to, and guarantee sufficient thermal conduction.Slide block play the guiding role, and guarantees can not touch in cooling copper wall moving process.Logical circulating liquid cooling fluid in cooling stud, the arrive-10oC of low temperature of assurance solid cooled device.
Accompanying drawing explanation
Fig. 1 is equipment schematic of the present invention.
1-unwrapping wire wheels, 2-top guide wheel, 3-regenerator section, 4-crucible, 5-heating unit, 6-cooling system, 7-bottom guide wheel, 8-take-up part, 9-vacuum system.
Fig. 2 is for putting a block position principle schematic.Unwrapping wire sectional shelf-unit is evenly fixed on a circumference of base plate, putting a synthetic fibre is fixed on and puts a sectional shelf-unit upper end, put and on a sectional shelf-unit, have a wheel bracket, during design, the envelope curve mother of the intersection point of wheel bracket and unwrapping wire sectional shelf-unit in spiral line is upper, the center of unwrapping wire guide wheel position corresponding to each actinobacillus wheel in spiral envelope curve.Like this each wire wheel, put a guide wheel and put between silk thread road and can not disturb.If unwrapping wire number is greater than 10, can around this principle on base plate, on the girth of the outer circle of 10 supports, place the suitable wire-unfolding rack of quantity, the unwrapping wire guide wheel at this moment increasing is put in first group of 10 guide wheels top successively according to same principle.
Fig. 3 is put the tenslator of a system.
The conduction of Fig. 4 solid thermal realizes cooling device.
Fig. 5 is for adopting 50 tungsten filaments prepared by the present invention to strengthen Zr
41.2ti
13.8cu
12.5ni
10.0be
22.5the cross section SEM photo of metal glass composite material silk.
Fig. 6 adopts 24 tungsten filaments prepared by the present invention to strengthen Zr
41.2ti
13.8cu
12.5ni
10.0be
22.5the cross section SEM photo of metal glass composite material silk.。
Fig. 7 is 50 and 24 tungsten filaments enhancing Zr that adopt the present invention to prepare
41.2ti
13.8cu
12.5ni
10.0be
22.5the X-ray diffractogram of metal glass composite material silk, the X-ray diffractogram of pure amorphous and pure tungsten silk as a comparison.
50 piece and the 24 piece tungsten filaments enhancing Zrs of Fig. 8 for adopting the present invention to prepare
41.2ti
13.8cu
12.5ni
10.0be
22.5the DSC thermal analysis curve figure of metal glass composite material silk, the DSC thermal analysis curve figure of pure amorphous as a comparison.
Embodiment
Embodiment 1:
Purity is greater than to 99.99% Zr, Ti, Cu, Ni and Be by nominal composition proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix the cooling ingot casting that obtains.Diameter is that the tungsten filament process of 80 μ m is removed surface film oxide through electrochemical etching in 5%NaOH solution, then in water, cleans.Tungsten filament after processing is wrapped on the guide wheel on haulage gear top, extension is loaded into bottom together with the mother alloy of pulverizing and is with in foraminate crucible, tungsten filament one end from-inner-to-outer is through the aperture of crucible, 820oC remelting Vit1 mother alloy insulation in process furnace, then by haulage gear by driven by motor the drop-down wire being immersed in melt of speed with V=30mm/s, make its surface uniform dipping one deck aluminium alloy, after passing heating zone, pass through the quick cooling formation coat of argon gas cold-trap, the final coated tungsten filament monofilament matrix material of metallic glass that obtains, and continuous winding is on the guide wheel of bottom.50 bunchys of monofilament after coating, evenly distribute is contained in respectively on six actinobacillus wheels, be wrapped in each guide roller of haulage gear top corresponding guide wheel on, extension is loaded into bottom together with the mother alloy of pulverizing and is with in foraminate crucible, tungsten filament Shu Yiduan from-inner-to-outer after coating is through the aperture of crucible, remelting mother alloy insulation in process furnace, then by haulage gear by driven by motor the drop-down wire bundle being immersed in melt of speed with V=10mm/s, make aluminium alloy at tungsten filament bundle surface and inner seepage flow, after passing heating zone, pass through the quick cooling formation metallic glass of argon gas cold-trap, the final tungsten that obtains strengthens zirconium-based metallic glass composite material, and continuous winding is on the guide wheel of bottom.The cross-sectional picture of matrix material, X-ray diffractogram (XRD) and thermal analysis curve figure (DSC) are respectively as shown in Fig. 5, Fig. 7 blue curve and Fig. 8 redness.As can be seen from Figure 5, the edge of tungsten filament is very clear smooth, does not occur significantly to dissolve and peel off, and the interface of matrix material is very bright and clean.As can be seen from Figure 7, the not compound obvious broadening of sample diffraction peak, is typical amorphous diffraction peak; In the diffraction spectra of matrix material, also can see this broad peak, only have above the diffraction crystal peak of tungsten filament is superimposed upon, and except the crystal peak corresponding to tungsten filament, there is no the corresponding diffraction peak of other crystalline state.Fig. 8 can find out, have obvious glass transition temp and crystallization temperature, and this composite silk and the corresponding glass transformation temperature of pure metal glass basically identical, further proved that the multi-cellular structure of preparation is comprised of pure amorphous phase.
Embodiment 2:
Technical scheme is as embodiment 1, in flow event, tungsten filament is selected 24 continuously, tungsten filament diameter is 80um, alloy remelting temperature is adjusted to 750oC, the pulling rate that regulates monofilament to apply is V=40mm/s, regulating the pulling rate in follow-up continuous flow event is V=20mm/s, and the tungsten filament that can obtain high-quality continuous production strengthens zirconium-based metallic glass composite material silk.Cross section SEM photo, X-ray diffractogram (XRD) and thermal analysis curve (DSC) are respectively as shown in Fig. 6, Fig. 7 red curve, Fig. 5 black curve.As can be seen from Figure 6, the edge of tungsten filament is very clear smooth, does not occur significantly to dissolve and peel off, and the interface of matrix material is very bright and clean.As can be seen from Figure 7, the not compound obvious broadening of sample diffraction peak, is typical amorphous diffraction peak; In the diffraction spectra of matrix material, also can see this broad peak, only have above the diffraction crystal peak of tungsten filament is superimposed upon, and except the crystal peak corresponding to tungsten filament, there is no the corresponding diffraction peak of other crystalline state.Fig. 8 can find out, have obvious glass transition temp and crystallization temperature, and this composite silk and the corresponding glass transformation temperature of pure metal glass basically identical, further proved that the multi-cellular structure of preparation is comprised of pure amorphous phase.
Claims (3)
1. a continuous production technique for fiber-reinforced metal glass composite material silk, is characterized in that:
(1) alloy preparing according to nominal composition is first smelted into uniform mother alloy with electric arc furnace, then mother alloy and wire is contained in to bottom and is with in foraminate crucible; (2) metallic glass alloys liquid applies single metal wire: single metal wire one end from-inner-to-outer is through the aperture of crucible, remelting mother alloy insulation in process furnace, then by haulage gear by the drop-down wire being immersed in melt of driven by motor, make its surface uniform dipping layer of metal glassy alloy liquid, cooling through aluminium alloy behind heating zone; (3) many one metal wires of metallic glass seepage flow process: the wire after primary coating is through actinobacillus wheel composition bundle or directly through an actinobacillus wheel bunchy, wire bundle one end from-inner-to-outer is through the aperture of crucible, remelting mother alloy insulation in process furnace, then by haulage gear by the drop-down wire bundle being immersed in melt of driven by motor, make its even Maceration alloy liquid, after passing heating zone, pass through the quick cooling formation metallic glass matrix of heat-eliminating medium; (4) the final fiber-reinforced metal glass composite material silk with higher-strength and certain stretch percentage elongation that obtains,
This continuous production technique equipment used is comprised of vacuum system (9), pre-heating system (3), heating system (5), cooling system (6), haulage gear, it is characterized in that haulage gear top is provided with unwrapping wire wheels (1), unwrapping wire wheels lower end is also provided with two unwrapping wire guide wheels (2), cooling system bottom is provided with a take-up guide wheel (7), unwrapping wire and take-up two guide wheel vertical directions are tangent, and bottom guide wheel is connected with motor, the silk of preparation directly can be wound up, realize continuously and producing; Cooling system (6) is tightly placed in crucible (4) bottom, guarantees that coated aluminium alloy rapid solidification forms metallic glass.
2. the continuous production technique of a kind of fiber-reinforced metal according to claim 1 glass composite material silk, wire is selected tungsten filament, and metallic glass alloys is selected zirconium base alloy.
3. the continuous production technique of a kind of fiber-reinforced metal according to claim 1 glass composite material silk, it is characterized in that: motor traction wire drawing speed is 1-70mm/s, the type of cooling of cooling system (6) is gas cold trap, heat of liquid conduction or solid thermal conduction+gas cold trap hybrid mode.
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| CN109082653A (en) * | 2017-06-13 | 2018-12-25 | 刘志红 | A kind of stainless steel/glass/copper clad composite filament and preparation method thereof |
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| CN101139689A (en) * | 2007-08-16 | 2008-03-12 | 北京科技大学 | Continuous preparation equipment and process for metal glass clad metal wire composite material |
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| CN2282553Y (en) * | 1996-11-19 | 1998-05-27 | 冯伟年 | Wire induction heater |
| CN101139689A (en) * | 2007-08-16 | 2008-03-12 | 北京科技大学 | Continuous preparation equipment and process for metal glass clad metal wire composite material |
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