CN102343374B - Apparatus and method for preparing micro-nano scaled metallic glass fiber - Google Patents
Apparatus and method for preparing micro-nano scaled metallic glass fiber Download PDFInfo
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- CN102343374B CN102343374B CN 201010241012 CN201010241012A CN102343374B CN 102343374 B CN102343374 B CN 102343374B CN 201010241012 CN201010241012 CN 201010241012 CN 201010241012 A CN201010241012 A CN 201010241012A CN 102343374 B CN102343374 B CN 102343374B
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Abstract
The invention relates to an apparatus and a method for preparing micro-nano scaled metallic glass fiber. According to the invention, a uniform master alloy ingot satisfying requirements is prepared by using an induction heating method or an electric arc melting method; the ingot is cast into a metallic glass rod by using a copper mould casting method, or is spun into a strap by using a vacuum melt-spinning machine; with a character of metallic glass that metallic glass can perform superplastic deformation in a supercooled liquid phase zone, the metallic glass rod or the strap is heated until the supercooled liquid phase zone is reached, and the rod or the strap is subject to superplastic deformation under traction forces, such that micro-nano scaled metallic glass fiber is obtained. With the apparatus and the method provided by the invention, micro-nano scale metallic glass fiber can be economically prepared with high efficiency. The prepared micro-nano scaled metallic glass fiber is continuous and uniform, and has high surface finish and controllable dimension.
Description
Technical field
The invention belongs to the condensed matter physics and materials science field.
Background technology
Glassy metal has mechanics and the functional characteristic of a lot of uniquenesses, and metallic glass fiber has caused the great interest of people especially.At present, metallic fiber and glass fibre are causing widely interest of people aspect engineering application and the scientific research.
Because glassy metal has supercooling liquid phase region as simple glass, can carry out superplastic forming, so the preparation method that glass fibre is used for reference in initial very natural the expecting of people prepares metallic glass fiber, but has no resolution all the time.This be because, on the one hand the Width unorganic glass of the supercooling liquid phase region of glassy metal is much smaller, thus in the process of processing easy crystallization and be difficult for carrying out superplastic deformation; On the other hand, glassy metal is less than lucite in the Factor of Brittleness of supercooling liquid phase region, so glassy metal changes very fast in the viscosity with temperature of supercooling liquid phase region, thereby there is not time enough to process, and along with the toughness of glassy metal is further improved (document 1, the Volkert of reducing of size, C.A., Donohue, A. ， ﹠amp; Spaepen, F.Effect of sample size on deformation in amorphous metals.J.Appl.Phys.103,083539 (2008) .), become especially glassy metal and move towards the major obstacle that engineering is used.So traditional glass fibre preparation technology can't be applied to prepare metallic glass fiber.
In the at present more common method for preparing metallic glass fiber, the preparation efficiency of metallic fiber is compared much lower with the preparation of glass fibre, and preparation cost is also high a lot, and dimensional controllability and the surface quality of metallic fiber can not show a candle to glass fibre.
As far back as 1981, the Inoue of northeastern Japan university adopts water to spin legal system standby micron order glassy metal silk (document 3, Inoue, A., Hagiwara, M. ， ﹠amp; Masumoto, T.Production of Fe-P-Camorphous wires by in-rotating-water spinning method and mechanical properties of the wires.J.Mater.Sci.17,580-588 (1981) .).But this method can not continuous production glassy metal silk, and the chemical reaction of melting foundry alloy and cooling fluid can't be avoided, and the glassy metal silk surface of this method preparation is oxidized, rough, and diameter is very inhomogeneous.
1991, Rudkowski invented melt and has got rid of a method (document 2, Rudkowski, P., Rudkowska, G.﹠amp; Strom-Olsen J.O.The fabrication of fine metallic fibers by continuous melt-extraction and their magnetic and mechanical properties.Mater.Sci.Engi.A133,158-161 (1991) .), the uniform micron order glassy metal of the method energy continuous production silk, and very even.But because contacting between blade and the silk, so that there is a groove on a thread surface.The another one continuously method of throwing is Taylor's method (document 3, Chiriac, H. ， ﹠amp;
T.A.Amorphousglass-covered magnetic wires:preparation, properties, applications.Prog.Mater.Sci.40,333-407 (1996) .), but this method also has a lot of shortcomings and limitations: and the fusion temperature of foundry alloy must be higher than the softening temperature of glass-coated thing; Thereby there is chemical reaction to cause the surperficial oxidized of glassy metal silk between glass-coated thing and the melting foundry alloy; The thermal coefficient of expansion of foundry alloy must with the approaching of glass-coated thing.More than these methods all can only do the glassy metal silk of 10～100 μ m.
2009, Kumar (document 4, Kumar, G., Tang, H.X.﹠amp; Schroers, J.Nanomoulding with amorphous metals.Nature 457,868-873 (2009) .) prepared the glassy metal line of diameter 13 nanometers with the method for nano impression, but its length only tens microns and surface quality are poor.The same year, Nakayama (document 5, Nakayama, K.S., Yokoyama, Y, Ono, T., Chen, M.W., Akiyama, K., Sakurai, T.﹠amp; Inoue A.Controlled formation and mechanical characterization of metallic glassy nanowires.Adv.Mater.21,1-4 (2009) .) go out nanoscale glassy metal silk with the quick traction legal system is standby, and this method is repeatable low, can not continuous production, and the longest only 1.3cm. of the length of glassy metal silk
Summary of the invention
The object of the invention is to substantially overcome the defective of above-mentioned prior art, thereby a kind of apparatus and method that can prepare efficiently, economically the micro/nano level metallic glass fiber are provided, and prepared micro/nano level metallic glass fiber is continuous, surface smoothness is high, size is controlled and even.
The invention provides a kind of device for preparing the micro/nano level metallic glass fiber, comprising:
-one Stainless steel chamber;
-one quartz glass tube and the stainless steel small column of placing with one heart; Described quartz glass tube is fixed on the Stainless steel chamber top inner surface by stationary fixture, its lower end closed and in the center one diameter to be arranged be the hole of 6～8mm; The height of described stainless steel small column is 2～6cm, and 2～6mm hole that the center has a diameter to be is to hold pending glassy metal base material;
-one high-frequency induction heating coil places the outside of described quartz glass tube;
-one pending glassy metal base material places the center hole of stainless steel small column;
-one counterweight is connected on the hook by draught line, and described hook links to each other bottom with the glassy metal base material;
-one prime mechanical pump and molecular pump group link to each other with described Stainless steel chamber lower end by butterfly valve, and described prime mechanical pump provides the low vacuum environment for molecular pump, and described molecular pump provides high vacuum environment for Stainless steel chamber;
-one high-purity argon gas cylinder links to each other with described Stainless steel chamber upper end by charging valve;
-take out mechanical pump on one side, link to each other with described Stainless steel chamber lower end by evacuating valve, be used for extracting the waste gas of described Stainless steel chamber.
The device of preparation micro/nano level metallic glass fiber provided by the invention, can also comprise and take in axle, it links to each other with motor, with a connecting line, one end of described connecting line is fixed on by fixture and takes on the axle, the other end links to each other with the lower end of glassy metal base material, takes in axle by motor drives and rotates, and the metallic glass fiber for preparing is wound in takes on the axle.
The method for preparing the micro-nano-scale metallic glass fiber provided by the invention is the traction method that the device at above-mentioned preparation micro-nano-scale metallic glass fiber carries out, and specifically comprises following step:
1) preparation one glassy metal base material: described glassy metal base material is served as reasons and is satisfied condition
The glassy metal bar or the band that make, wherein m is the Factor of Brittleness of subcooled liquid, Δ T is the supercooling liquid phase region width, T
xBe crystallization temperature, by the amorphous formation ability of its foundry alloy that makes greater than 20 μ m;
Described glassy metal bar is roughly the cylindrical of diameter 0.5～3mm, long 2～6cm, leave diameter greater than the clout of stainless steel small column center hole at the one end, unlikely the sliding so that this metal base can be positioned in the center hole of stainless steel small column;
The width of described glassy metal band is that 0.1～3mm, length are 2～6cm;
2) with step 1) the glassy metal base material that makes places the center hole of the stainless steel small column of foregoing device, put it into again in the quartz glass tube and with stationary fixture this quartz glass tube is fixed on the Stainless steel chamber top inner surface, make this stainless steel small column be positioned at the centre of high-frequency induction heating coil, notice that glassy metal bar or band must not contact with the inwall of the center hole of stainless steel small column, to avoid destroying the surface quality of the metallic glass fiber that makes; One counterweight is received the glassy metal base material bottom by draught line and hook connecting;
3) take out mechanical pump by the side Stainless steel chamber is evacuated to 10Pa, close the other valve that mechanical pump links to each other with Stainless steel chamber of taking out; Continue that by prime mechanical pump and molecular pump group Stainless steel chamber is evacuated to vacuum and be equal to or higher than 10
-3Pa closes the butterfly valve that this prime mechanical pump and molecular pump group link to each other with Stainless steel chamber; Be filled with again high-purity (99.999%) argon gas 0.02MPa; Heat under the electric current of 12A with radio-frequency induction coil; When the glassy metal base material was heated to its supercooling liquid phase region, the viscosity of glassy metal base material descended; When viscosity dropped to metal base and again props up the gravity of the counterweight that is unable to hold out, superplastic deformation will occur in the glassy metal base material, and therefore counterweight also descends thereupon, makes a metallic glass fiber.
The apparatus and method of preparation micro/nano level metallic glass fiber of the present invention are to prepare a master alloy ingot that satisfies condition uniformly with the method for eddy-current heating or electric arc melting first, then with copper mold casting method it is cast the glassy metal bar or get rid of the band machine with vacuum and get rid of into band, utilized at last glassy metal can carry out in its supercooling liquid phase region the characteristic of superplastic deformation, heating of metal glass bar or bar bring to its supercooling liquid phase region and under the draw of power (the gravity traction effect of counterweight or the draw of taking in axle) make it carry out superplastic deformation, thereby obtain the metallic glass fiber of micro-nano-scale, compared with prior art, the present invention has following advantage:
1, the preparation method is simple, efficient is high, preparation cost is very low;
2, the metallic glass fiber of prepared micro/nano level evenly, continuously, any surface finish, size be controlled, can weave and have excellent mechanics and functional characteristic, this makes it in fields such as micro-nano mechanical system, composite, sensor, smart fabric, integrated circuit connection, micro-nano conductor, armored fabric and waveguide wires very strong practical value be arranged.
Description of drawings
Fig. 1 is the schematic diagram of the device of preparation micro/nano level metallic glass fiber according to an embodiment of the present invention;
Fig. 2 is the schematic diagram of device of the long metallic glass fiber of preparation micro/nano level of another embodiment according to the present invention;
Fig. 3 is the micro/nano level metallic glass fiber Zr of the embodiment of the invention 1 preparation
35Ti
30Be
27.5Cu
7.5(B) and the Pd of embodiment 2 preparation
40Cu
30Ni
10P
20(A) XRD;
Fig. 4 is the stereoscan photograph of various fibers, and wherein Fig. 4 a is the Pd of 316L stainless steel fibre (A), the embodiment of the invention 4 preparations
40Cu
30Ni
10P
20Metallic glass fiber (B) and silica glass fiber (C) surface quality are relatively; Fig. 4 b is the uniform long Pd of embodiment 2 preparations
40Cu
30Ni
10P
20Metallic glass fiber, illustration have shown the best bright finish of metallic glass fiber; Fig. 4 c and Fig. 4 d are respectively that the diameter of embodiment 4 preparations is the metallic glass fiber of 279nm and the metallic glass fiber of the 74nm that embodiment 5 prepares;
Fig. 5 is the comparison diagram of the bending resistance of various fibers, and wherein: Fig. 5 a is the 316L stainless steel fibre, and Fig. 5 b is the Pd of embodiment 4
40Cu
30Ni
10P
20Metallic glass fiber, Fig. 5 c are the silica glass fiber;
Fig. 6 is the micro/nano level metallic glass fiber Zr of the embodiment of the invention 1 preparation
35Ti
30Be
27.5Cu
7.5Tensile stress strain curve;
Fig. 7 is the micro/nano level metallic glass fiber Zr of the embodiment of the invention 1 preparation
35Ti
30Be
27.5Cu
7.5The diameter of metallic glass fiber and the relation curve between the tractive force;
Wherein:
1 Stainless steel chamber, 2 stationary fixtures, 3 quartz glass tubes
4 high-frequency induction heating coils, 5 stainless steel small columns, 6 glassy metal base materials
7 draught lines, 8 counterweights, 9 butterfly valves
10 prime mechanical pumps and molecular pump group 11 argon gas charging valves 12 evacuating valves
13 other mechanical pump 14 motor 15 fixtures of taking out
16 connecting lines 17 are taken in axle 18 hooks.
The specific embodiment
The device of preparation micro/nano level metallic glass fiber provided by the invention as shown in Figure 1, comprising:
-one Stainless steel chamber 1 (vacuum chamber), the various shapes such as that this Stainless steel chamber can be is cylindrical, cube, spheroidal;
-one quartz glass tube 3 (also can be earthenware or graphite-pipe) and the stainless steel small column 5 of placing with one heart; Described quartz glass tube 3 is fixed on Stainless steel chamber 1 top inner surface by stationary fixture 2, its lower end closed and in the center one diameter to be arranged be the hole of 6～8mm; Described stainless steel small column is shelved on the lower end of quartz glass tube steel, and it highly is 2～6cm, and one diameter is arranged is 2～6mm hole in the center, to hold pending glassy metal base material 6;
-one high-frequency induction heating coil 4 places the outside of described quartz glass tube 3;
-one pending glassy metal base material 6 places the center hole of stainless steel small column 5;
-one counterweight 8 is connected on a hook 18 (not shown) by draught line 7, and described hook 18 links to each other bottom with glassy metal base material 6, and preferably, the weight of described counterweight 8 is 0.01～500g; When the glassy metal base material is heated to its supercooling liquid phase region, the viscosity of glassy metal base material 6 descends, until the glassy metal base material that this viscosity descends is when again propping up the gravity of the counterweight that is unable to hold out, superplastic deformation will occur in the glassy metal base material, and therefore counterweight also descends thereupon;
-one prime mechanical pump and molecular pump group 10 link to each other with described Stainless steel chamber lower end by butterfly valve 9, and described prime mechanical pump provides the low vacuum environment for molecular pump, and described molecular pump provides high vacuum environment for Stainless steel chamber;
-one high-purity argon gas cylinder (not shown) links to each other with described Stainless steel chamber upper end by charging valve 11;
-take out mechanical pump 13 on one side, link to each other with described Stainless steel chamber lower end by evacuating valve 12, be used for extracting the waste gas of described Stainless steel chamber; Because molecular pump can only could move under air pressure is lower than the environment of 10Pa, the side is taken out mechanical pump and can be extracted into Stainless steel chamber below the 10Pa before prime mechanical pump and molecular pump group pumping high vacuum.
In one embodiment of the present invention, when needing the metallic glass fiber of preparation length, as shown in Figure 2, the device of preparation micro/nano level metallic glass fiber provided by the invention also comprises takes in axle 17, and it links to each other with motor 14, and a connecting line 16, one end of described connecting line is fixed on by fixture 15 and takes on the axle 17, the other end links to each other with the lower end of glassy metal base material 6, takes in axle by motor drives and rotates, and the metallic glass fiber for preparing is wound in takes on the axle; And counterweight descends thereupon and when finally dropping on the bottom of Stainless steel chamber, hook breaks off relations from the glassy metal base material, takes on the axle thereby avoided counterweight to be wrapped in.
The method that the present invention prepares the micro-nano-scale metallic glass fiber is on the device of above-mentioned preparation micro-nano-scale metallic glass fiber the glassy metal base material to be carried out the traction method, specifically comprises following step:
1) preparation one glassy metal base material: described glassy metal base material is served as reasons and is satisfied condition
The glassy metal bar or the band that make, wherein m is the Factor of Brittleness of subcooled liquid, Δ T is the supercooling liquid phase region width, T
xBe crystallization temperature, greater than 20 μ m, detailed process is by the amorphous formation ability of its foundry alloy that makes:
With the atomic ratio batching of high-purity (＞99.9%) element by required glassy metal, put it in the electric arc furnaces; Be evacuated to vacuum and be equal to or higher than 10
-3Pa is filled with high-purity (99.999%) argon gas, will vacuumize-being cycled to repeat several times of applying argon gas; Then melting titanium ingot makes it absorb oxygen remaining in the furnace chamber; The melt back foundry alloy makes it even four to six times again, cools off, and obtains the master alloy ingot of required glassy metal;
Then according to conventional method with described master alloy ingot again melting and inhale cast onto in the water cooled copper mould, obtain the bar of the glassy metal of diameter 0.5～3mm, long 2～6cm, one end unlikely the sliding of staying diameter greater than the clout of stainless steel small column center hole so that this metal base can be positioned in the center hole of stainless steel small column; Perhaps
Described master alloy ingot is put into a quartz glass tube with spout, this quartz glass tube is installed in vacuum gets rid of with in the load coil in the machine furnace chamber, make the about 1mm of distance of the mouth of pipe and copper wheel; Be evacuated to vacuum and be equal to or higher than 10
-3Pa is filled with high-purity (99.999%) argon gas of 0.02MPa, sets simultaneously the speed of copper wheel rotation; The power supply of opening load coil heats this foundry alloy to fully fusing, open to drive the switch of the motor of copper wheel rotation, press the argon gas gas-filled switching tube when speed for the treatment of the copper wheel rotation reaches preset value and make the foundry alloy liquid ejection of fusing and form the glassy metal band; Cutting width from these bands is that 0.1～3mm, length are that the band of 2～6cm is as the glassy metal base material;
2) with step 1) the glassy metal base material that makes places the center hole of stainless steel small column of the device of foregoing preparation micro-nano-scale metallic glass fiber of the present invention, put it into again in the quartz glass tube and with stationary fixture this quartz glass tube is fixed on the Stainless steel chamber top inner surface, make this stainless steel small column be positioned at the centre of high-frequency induction heating coil, notice that glassy metal bar or band must not contact with the inwall of the center hole of stainless steel small column, to avoid destroying the surface quality of the metallic glass fiber that makes; One counterweight is received the glassy metal base material bottom by draught line and hook connecting;
3) take out mechanical pump by the side Stainless steel chamber is evacuated to 10Pa, close the other valve that mechanical pump links to each other with Stainless steel chamber of taking out; Continue that by prime mechanical pump and molecular pump group Stainless steel chamber is evacuated to vacuum and be equal to or higher than 10
-3Pa closes the butterfly valve that this prime mechanical pump and molecular pump group link to each other with Stainless steel chamber; Be filled with again high-purity (99.999%) argon gas 0.02MPa; Heat under the electric current of 12A with radio-frequency induction coil; When the glassy metal base material was heated to its supercooling liquid phase region, the viscosity of glassy metal base material descended; When viscosity dropped to metal base and again props up the gravity of the counterweight that is unable to hold out, superplastic deformation will occur in the glassy metal base material, and therefore counterweight also descends thereupon, makes a metallic glass fiber.If when needing long metallic glass fiber, can be when counterweight begins to descend, open motor, drive is taken in axle and is rotated, prepared metallic glass fiber is wound in takes on the axle, and at this moment counterweight is linked up with from the glassy metal base material and is broken off relations in the initial bottom that descends and finally drop on Stainless steel chamber thereupon, does not take on the axle thereby counterweight can not be wrapped in.
1) purity greater than 99.9% Zr, Ti, Be and Cu according to Zr
35Ti
30Be
27.5Cu
7.5(at.%) atomic ratio prepares raw material, then puts it in the electric arc furnaces.Be evacuated to 10
-3Below the Pa, be filled with high-purity (99.999%) argon gas, vacuumize again again applying argon gas, triplicate like this, after then melting titanium ingot made it absorb oxygen remaining in furnace chamber, the melt back foundry alloy was four times again, make it even, cool off at last, obtain the master alloy ingot of required glassy metal.
2) an amount of fritter master alloy ingot is put in the electric arc furnaces, again carries out melting and inhale casting onto in the water cooled copper mould under the protection of high-purity argon gas, obtaining diameter is 1mm, is about the Zr of 3cm
35Ti
30Be
27.5Cu
7.5Glassy metal rod leaves oblate spheroid shape clout (diameter is greater than stainless steel small column center hole) in order to the glassy metal rod is placed in the center hole of stainless steel small column 5 at the head of glassy metal rod.
Glassy metal rod or band that this makes satisfy condition
Wherein the Factor of Brittleness m of subcooled liquid is 37, and the width Delta T of supercooling liquid phase region is 147K, and crystallization temperature is 731K, and the amorphous formation ability of described foundry alloy is greater than 20 μ m.
This glassy metal rod is installed in the center hole (diameter is the hole of 2.5mm) of stainless steel small column 5 (highly for 4cm) of device shown in Figure 1, put it into again in the quartz glass tube 3 (its lower end closed and one diameter is arranged in the center be the hole of 5mm) and this quartz glass tube is fixed on Stainless steel chamber 1 top inner surface with stationary fixture 2, make this stainless steel small column 5 be positioned at the centre of high-frequency induction heating coil 4, notice that the glassy metal rod must not contact with the inwall of the center hole of stainless steel small column, to avoid destroying the surface quality of the metallic glass fiber that makes; The counterweight 8 of one 50g is connected to the glassy metal rod bottom by draught line 7 and hook 18.
3) open evacuating valve 12 and take out mechanical pump 13 with the side Stainless steel chamber is evacuated to about 10Pa, close evacuating valve 12; Open butterfly valve 9, and continue Stainless steel chamber is evacuated to 10 with prime mechanical pump and molecular pump group 10
-3Pa closes butterfly valve; Open again argon gas charging valve 11 and be filled with high-purity (99.999%) argon gas 0.02MPa; Heat under the electric current of 12A with radio-frequency induction coil.When the glassy metal rod was heated to its supercooling liquid phase region, its viscosity descended.When viscosity dropped to the glassy metal rod and again props up the gravity of the counterweight that is unable to hold out, superplastic deformation will occur in this glassy metal rod, and therefore counterweight also descends thereupon, thereby formed Zr
35Ti
30Be
27.5Cu
7.5Metallic glass fiber.
This Zr
35Ti
30Be
27.5Cu
7.538 microns of the diameters of metallic glass fiber, length are 215mm.Its X-ray diffraction (XRD) is shown in the curve B among Fig. 3, can find out, except roomy dispersing the peak, there is not the corresponding sharp-pointed bragg peak of crystal on the XRD diffraction pattern, be single amorphous phase so draw the prepared metallic glass fiber of method with power of the present invention.The glass transformation temperature of this metallic glass fiber is 584K, and the width Delta T of supercooling liquid phase region is 147K, and crystallization temperature is 731K.Its tensile stress strain curve as shown in Figure 6.Strain rate, Young's modulus, fracture strength and breaking strain are respectively 2 * 10
-4s
-1, 94GPa, 1765MPa, 1.88%.
Similarly, with the glassy metal rod of 1 millimeter of above-mentioned diameter as base material, respectively with 10 grams, 20 grams, 50 grams and 110 gram counterweights as tractive force (respectively corresponding 0.1 newton, 0.2 newton, 0.5 newton and 1.1 newton), prepare the Zr that diameter is respectively 10 microns, 12 microns, 38 microns and 108 microns
35Ti
30Be
27.5Cu
7.5Metallic glass fiber, the corresponding relation of tractive force and metallic glass fiber diameter is plotted in Fig. 7.Can find out that if substrate diameter is identical, then tractive force is larger, then the metallic glass fiber of preparation is thicker, but this corresponding relation is not linear.This rule also is applicable to prepare the metallic glass fiber of other compositions.
1) purity greater than 99.9%Pd, Cu, Ni according to Pd
40Cu
30Ni
10P
20(at.%) composition proportion prepares raw material.Then such as the step 1 among the embodiment 1) Pd, Cu, Ni melting are obtained Pd
40Cu
30Ni
10Master alloy ingot.Take by weighing Pd with assay balance
40Cu
30Ni
10The quality a of alloy pig is according to Pd
40Cu
30Ni
10P
20(at.%) composition proportion calculates the quality m of P.Take by weighing quality and be 1.2～1.3 times to the high purity phosphorus of m, and and Pd
40Cu
30Ni
10Alloy pig is enclosed in the high vacuum quartz glass tube together, then drops it off vacuum and gets rid of and carry out melting in the band machine.Weigh the quality m ' of resulting alloy pig, then the quality of phosphorus is m '-a in this alloy pig.According to Pd
40Cu
30Ni
10P
20(at.%) composition proportion calculates the corresponding Pd of phosphorus that quality is m '-a
40Cu
30Ni
10Quality a ', adding quality in alloy pig is the Pd of a '-a
40Cu
30Ni
10And get rid of in vacuum and to carry out melting in the band machine to obtain composition proportion be Pd
40Cu
30Ni
10P
20Alloy pig.
2) such as the step 2 among the embodiment 1) the preparation diameter is 1 millimeter Pd
40Cu
30Ni
10P
20The glassy metal rod, the glassy metal rod that this foundry alloy makes satisfies condition
Wherein the Factor of Brittleness m of subcooled liquid is 59.
3) in such as the device among the embodiment 1, with hanging the counterweights of one 1 grams under the above-mentioned glassy metal rod base material, then according to the step 3 among the embodiment 1) to prepare a diameter be 5 microns, length is the Pd of 215mm
40Cu
30Ni
10P
20Metallic glass fiber.Its X-ray diffraction (XRD) can find out except roomy dispersing the peak, do not have the corresponding sharp-pointed bragg peak of crystal on the XRD diffraction pattern shown in the curve A among Fig. 3, so draw the prepared Pd of method with power of the present invention
40Cu
30Ni
10P
20Metallic glass fiber is single amorphous phase.The glass transformation temperature of this metallic glass fiber is 572K, and the width Delta T of supercooling liquid phase region is 98K, and crystallization temperature is 670K, and the amorphous formation ability of this foundry alloy is greater than 20 μ m.Its outward appearance stereoscan photograph is seen Fig. 4 b.
1) purity greater than 99.9% Cu, Gd according to Cu
25Gd
10(at.%) composition proportion prepares raw material.Then use the step 1 among the embodiment 1) the same method obtains Cu with Cu, Gd melting
25Gd
10Master alloy ingot.
2) with Cu
25Gd
10Master alloy ingot is broken into fritter.Take by weighing Cu about about 1g with the precise electronic balance
25Gd
10The quality of foundry alloy, and press Mg
65Cu
25Gd
10(at.%) composition proportion calculates the quality of Mg.With load weighted Cu
25Gd
10Foundry alloy and Mg put into the quartz glass tube of band circle spout together, it is installed in vacuum gets rid of in the band machine, and allow spout align with blowhole on the copper mold.Be evacuated to 10
-3Below the Pa, pour high-purity (99.999%) argon gas of 0.02MPa.Then carry out eddy-current heating.When alloy melting evenly after, open gas-filled switching tube and the liquid of fusing sprayed into to obtain diameter among the copper mold be 1mm, be about the Mg of 2.5cm
65Cu
25Gd
10The glassy metal rod.The glassy metal rod that this foundry alloy makes satisfies condition
Wherein the Factor of Brittleness m of subcooled liquid is 41.
3) in such as the device among the embodiment 1, with hanging the counterweights of one 20 grams under the above-mentioned glassy metal rod base material, such as the step 3 among the embodiment 1) to prepare diameter be 49 microns, length is 215 millimeters Mg
65Cu
25Gd
10Metallic glass fiber.The glass transformation temperature of this metallic glass fiber is 406K, and the width Delta T of supercooling liquid phase region is 82K, and crystallization temperature is 488K, and the amorphous formation ability of this foundry alloy is greater than 20 μ m.
Embodiment 4, preparation diameter are the Pd of 279 nanometers
40Cu
30Ni
10P
20Metallic glass fiber
1) method according to embodiment 2 prepares first the Pd that a diameter is 5 μ m
40Cu
30Ni
10P
20Metallic glass fiber.
2) cutting length is long one section of 3cm, places the as shown in Figure 1 stainless steel small column of device, 1.5 millimeters of its center-hole diameters, and with the counterweight of a 0.5g by draught line with link up with it bottom.Then by the step 3 among the embodiment 1) this metallic glass fiber is carried out the secondary superplastic forming, obtain the Pd that diameter is 279 nanometers
40Cu
30Ni
10P
20Metallic glass fiber, its outward appearance stereoscan photograph is seen Fig. 4 c.
Fig. 4 a shows the Pd of 316L stainless steel fibre (A), present embodiment preparation
40Cu
30Ni
10P
20Metallic glass fiber (B) and silica glass fiber (C) surface quality are relatively, by clearly visible among the figure, the smooth surface of metallic glass fiber (B), even, its surface flatness can be compared U.S. with glass fibre (C) with uniformity, and will get well more than stainless steel fibre (A), namely metallic glass fiber of the present invention has best bright finish.Because the size of metallic glass fiber of the present invention still has high surface flatness and uniformity after reaching nanoscale, so this smooth uniform metallic glass fiber is the reliable material of making accurate micro-nano device.And the performance reduction of existing stainless steel fibre fiber because its inhomogeneities and blemish are removed also causes fiber thickness uneven, so that measure difficult and inaccurate when using, the very difficult analysis of the measurement result of its acquisition and unreliable.
Embodiment 5, preparation diameter are the Pd of 74 nanometers
40Cu
30Ni
10P
20Metallic glass fiber
1) according to the step 1 of embodiment 2) preparation Pd
40Cu
30Ni
10P
20Master alloy ingot also is broken into fritter.
2) with an amount of Pd
40Cu
30Ni
10P
20The foundry alloy fritter is put into the quartz glass tube with spout.Quartz glass tube is installed in a vacuum gets rid of in the furnace chamber with machine, the about 1mm of distance of the mouth of pipe and copper wheel.Be evacuated to 10
-3Below the Pa, pour high-purity (99.999%) argon gas of 0.02MPa, set simultaneously the plastics of copper wheel rotation.The heating foundry alloy is opened the copper wheel rotary switch to fully fusing, opens gas-filled switching tube when the speed for the treatment of the copper wheel rotation reaches preset value and makes the foundry alloy liquid ejection of fusing and form band.
3) cutting length from band is Pd below the wide 0.2mm of 3cm
40Cu
30Ni
10P
20The glassy metal band places the stainless steel small column (1.5 millimeters of its center-hole diameters) of the device shown in the embodiment 1, with 0.5 gram counterweight traction, then according to embodiment 1 step 3), obtain the Pd that diameter is 74 nanometers
40Cu
30Ni
10P
20Metallic glass fiber, its outward appearance stereoscan photograph is seen Fig. 4 d.
The Pd of embodiment 6,20 microns of diameters of preparation
40Cu
30Ni
10P
20Metallic glass fiber
For the bending resistance between the more different fibers, present embodiment has prepared 20 microns of diameters, long 215 millimeters Pd
40Cu
30Ni
10P
20Metallic glass fiber.The preparation method is fully with embodiment 2, and equipment therefor and device parameter thereof are with embodiment 1, and unique difference is to use 15 gram counterweights.The thermal physical property parameters such as its glass transformation temperature, supercooling liquid phase region width and crystallization temperature are identical with embodiment 2.
The bending resistance comparison diagram of three kinds of fibers as shown in Figure 5, wherein a is stainless steel fibre, and it has very strong bending resistance, and the deformation pattern at its angle of bend place is homogeneous deformation; B is the Pd of 20 microns of diameters
40Cu
30Ni
10P
20Metallic glass fiber, its bending resistance are also very strong, and this is owing to the formation of the high density shear band at angle of bend place; C is glass fibre, and it is easy to be fractureed.
1) according to the step 1 of embodiment 1) method prepare La
57.5Cu
12.5Ni
12.5Al
17.5Foundry alloy.
Glassy metal rod or band that this foundry alloy makes satisfy condition
Wherein the Factor of Brittleness m of subcooled liquid is 55.
2) according to the step 2 of embodiment 1) method prepare La
57.5Cu
12.5Ni
12.5Al
17.5The glassy metal rod.
3) in order to obtain long metallic glass fiber, La
57.5Cu
12.5Ni
12.5Al
17.5The glassy metal rod is installed in the Stainless steel chamber according to shown in Figure 2, its lower end is except with the counterweight of 1g links to each other, also by connecting another connecting line 16, the other end of this connecting line is fixed on by fixture 15 and takes on the axle 17, take in axle 17 and link to each other with motor 14, take in axle by motor drives and rotate.
Then, open evacuating valve 12 and take out mechanical pump 13 with the side Stainless steel chamber is evacuated to about 10Pa, close evacuating valve 12; Open butterfly valve 9, and continue Stainless steel chamber is evacuated to 10 with prime mechanical pump and molecular pump group 10
-3Pa closes butterfly valve; Open again argon gas charging valve 11 and be filled with high-purity (99.999%) argon gas 0.02MPa; Heat under the electric current of 12A with radio-frequency induction coil.When the glassy metal rod was heated to its supercooling liquid phase region, its viscosity descended.Under the effect of Weight gravity, the glassy metal rod carries out superplastic deformation, and counterweight moves down.When counterweight begins to descend, start immediately simultaneously to drive and take in the motor 14 that axle 17 rotates, velocity of motor is set to 20 meter per seconds.Metallic glass fiber is wrapped in to be taken on the axle 17, and counterweight connects hook and comes off (breaking off relations from the glassy metal base material) in the initial bottom that descends and finally drop on Stainless steel chamber thereupon, thereby counterweight can not be wrapped on the bearing of taking in axle.
In the present embodiment, the La that makes
57.5Cu
12.5Ni
12.5Al
17.5The metallic glass fiber diameter is 74 nanometers, and length is 264 millimeters.Without doubt, also can as required, prepare longer metallic glass fiber.
Its glass transformation temperature is 435K, and the width Delta T of supercooling liquid phase region is 75K, and crystallization temperature is 510K, and the amorphous formation ability of this foundry alloy is greater than 20 μ m.
Claims (10)
1. device for preparing the micro/nano level metallic glass fiber comprises:
-one Stainless steel chamber;
-one quartz glass tube and the stainless steel small column of placing with one heart; Described quartz glass tube is fixed on the Stainless steel chamber top inner surface by stationary fixture, its a lower end closed and hole is arranged in the center; There is a hole described stainless steel small column center, to hold pending glassy metal base material;
-one high-frequency induction heating coil places the outside of described quartz glass tube;
-one pending glassy metal base material places the center hole of stainless steel small column;
-one counterweight is connected on the hook by draught line, and described hook links to each other bottom with the glassy metal base material;
-one prime mechanical pump and molecular pump group link to each other with described Stainless steel chamber lower end by butterfly valve, and the prime mechanical pump in the described pump group provides the low vacuum environment for the molecular pump in the described pump group, and described molecular pump provides high vacuum environment for Stainless steel chamber;
-one high-purity argon gas cylinder links to each other with described Stainless steel chamber upper end by charging valve;
-take out mechanical pump on one side, link to each other with described Stainless steel chamber lower end by evacuating valve, be used for extracting the waste gas of described Stainless steel chamber.
2. device as claimed in claim 1, it is characterized in that: also comprise and take in axle, it links to each other with motor; With a connecting line, an end of described connecting line is fixed on by fixture and takes on the axle, and the other end links to each other with the lower end of glassy metal base material, takes in axle by motor drives and rotates, and the metallic glass fiber for preparing is wound in takes on the axle.
3. such as the device of claim 1 or 2, it is characterized in that: the diameter in the hole of described quartz glass tube center is 6～8mm.
4. such as the device of claim 1 or 2, it is characterized in that: the height of described stainless steel small column is 2～6cm, and the diameter of the hole of the center is 2～6mm.
5. such as the device of claim 1 or 2, it is characterized in that: the weight of described counterweight is 0.01～500g.
6. a method for preparing the micro-nano-scale metallic glass fiber is the traction method that the described device of arbitrary claim in claim 1-5 carries out, and comprises following step:
1) preparation one glassy metal base material: described glassy metal base material is served as reasons and is satisfied condition
The glassy metal bar or the band that make, wherein m is the Factor of Brittleness of subcooled liquid, Δ T is the supercooling liquid phase region width, T
xBe crystallization temperature, by the amorphous formation ability of its foundry alloy that makes greater than 20 μ m;
Described glassy metal bar is one cylindrical, leaves diameter greater than the clout of stainless steel small column center hole at the one end, unlikely the sliding so that this glassy metal base material can be positioned in the center hole of stainless steel small column;
2) the glassy metal base material that step 1) is made places the center hole of the stainless steel small column of described device, put it into again in the quartz glass tube and with stationary fixture this quartz glass tube is fixed on the Stainless steel chamber top inner surface, make this stainless steel small column be positioned at the centre of high-frequency induction heating coil; One counterweight is received the glassy metal base material bottom by draught line and hook connecting;
3) take out mechanical pump by the side Stainless steel chamber is evacuated to 10Pa, close the other valve that mechanical pump links to each other with Stainless steel chamber of taking out; Continue that by prime mechanical pump and molecular pump group Stainless steel chamber is evacuated to vacuum and be equal to or higher than 10
-3Pa closes the butterfly valve that this prime mechanical pump and molecular pump group link to each other with Stainless steel chamber; Be filled with again high-purity argon gas 0.02MPa; Heat under the electric current of 12A with radio-frequency induction coil; When the glassy metal base material was heated to its supercooling liquid phase region, the viscosity of glassy metal base material descended; When viscosity dropped to the glassy metal base material and again props up the gravity of the counterweight that is unable to hold out, superplastic deformation will occur in the glassy metal base material, and therefore counterweight also descends thereupon, makes a metallic glass fiber.
7. method as claimed in claim 6, wherein said glassy metal bar are the cylindrical of diameter 0.5～3mm, long 2～6cm.
8. method as claimed in claim 6, the width of wherein said glassy metal band is that 0.1～3mm, length are 2～6cm.
9. method as claimed in claim 6 wherein also comprises a step: when when counterweight begins to descend, open motor, drive and take in the axle rotation, prepared metallic glass fiber is wound in takes on the axle.
10. such as claim 6 or 9 described methods, the weight of wherein said counterweight is 0.01～500g.
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| CN104342606A (en) * | 2013-07-31 | 2015-02-11 | 中国科学院物理研究所 | Device and method for manufacturing amorphous alloy wires |
| CN104772361A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of amorphous alloy fiber and device for implementing the preparation method |
| CN106927420B (en) * | 2015-12-29 | 2018-11-27 | 中国科学院物理研究所 | A method of preparing the three-dimensional sight device that is situated between |
| CN107686951A (en) * | 2017-09-08 | 2018-02-13 | 张家港创博金属科技有限公司 | Nano metal glass thread preparation method |
| CN112126871A (en) * | 2020-04-07 | 2020-12-25 | 上海大学 | Device and method for preparing micro-nano metal glass tube |
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| CN101050075A (en) * | 2007-05-10 | 2007-10-10 | 彭书成 | Composite materials of modified fiber material of amorphous alloy and concrete |
| CN101532117A (en) * | 2008-03-12 | 2009-09-16 | 中国科学院金属研究所 | Continuous metallic glass fiber and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101050075A (en) * | 2007-05-10 | 2007-10-10 | 彭书成 | Composite materials of modified fiber material of amorphous alloy and concrete |
| CN101532117A (en) * | 2008-03-12 | 2009-09-16 | 中国科学院金属研究所 | Continuous metallic glass fiber and preparing method thereof |
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| 余鹏等.具有优良玻璃形成能力添加Al的CuZr基大块金属玻璃.《物理学报》.2005,第54卷(第7期),全文. |
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