CN106488809B - Manufacture the method and system of block metal glass sheet material - Google Patents
Manufacture the method and system of block metal glass sheet material Download PDFInfo
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- CN106488809B CN106488809B CN201480073984.4A CN201480073984A CN106488809B CN 106488809 B CN106488809 B CN 106488809B CN 201480073984 A CN201480073984 A CN 201480073984A CN 106488809 B CN106488809 B CN 106488809B
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- 239000002184 metal Substances 0.000 title claims abstract description 153
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 153
- 239000011521 glass Substances 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 108
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims description 156
- 238000005096 rolling process Methods 0.000 claims abstract description 109
- 238000002425 crystallisation Methods 0.000 claims abstract description 40
- 230000008025 crystallization Effects 0.000 claims abstract description 40
- 239000005300 metallic glass Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims description 83
- 238000010438 heat treatment Methods 0.000 claims description 81
- 238000012545 processing Methods 0.000 claims description 54
- 230000008569 process Effects 0.000 claims description 28
- 230000007246 mechanism Effects 0.000 claims description 20
- 230000001965 increasing effect Effects 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 238000004781 supercooling Methods 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 2
- 241001131688 Coracias garrulus Species 0.000 claims 13
- 230000009471 action Effects 0.000 claims 1
- 239000013526 supercooled liquid Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 abstract description 4
- 238000005098 hot rolling Methods 0.000 description 27
- 239000000956 alloy Substances 0.000 description 14
- 230000002706 hydrostatic effect Effects 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 238000009740 moulding (composite fabrication) Methods 0.000 description 11
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 10
- 238000005266 casting Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000007711 solidification Methods 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
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- 238000000071 blow moulding Methods 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- 238000010420 art technique Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/003—Making ferrous alloys making amorphous alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
- B21B27/06—Lubricating, cooling or heating rolls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J1/00—Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
- B21J1/003—Selecting material
- B21J1/006—Amorphous metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/003—Amorphous alloys with one or more of the noble metals as major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/005—Amorphous alloys with Mg as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
The present disclosure describe how deform glassy metal under the conditions of low power and stabilisation to manufacture thin and method and hardware of large-area metal glass sheet.Its combination based on thermoplasticity rolling and stretching, and normally in conjunction with preheating method.The Main Patterns of deformation depend on BMG condition such as thickness, viscosity and crystallization time.
Description
Cross reference to related applications
61/919, the 158 and 2014 year July 17 of U.S. Provisional Application No. submitted this application claims on December 20th, 2013
The equity of number U.S. Provisional Application No. 62/025,558 submitted, their own theme pass through reference in its entirety simultaneously herein
Enter.
Invention field
The present invention relates generally to deform glassy metal to manufacture the method for glassy metal sheet material, web and band and set
It is standby.
Statement about federally funded research or development
The present invention is to be made according to the W911NF-11-I-0380 authorized at US Army research using governmental support.
U.S. government has certain rights in the present invention.
Background of invention
Block metal glass (BMG), is also referred to as bulk-solidifying amorphous composition, is a kind of amorphous metal
Alloy material is considered as the promising material for broad spectrum application, this is because their excellent properties are for example
High-yield strength, big elastic strain limit and highly corrosion resistant.
The peculiar property of BMG is that they have supercooling liquid phase region (SCLR), and Δ Tsc is viscous liquid state
(regime) relative measurement of stability.The glass transition temperature Tg of SCLR Tx and specific BMG alloy by crystallization
Between temperature difference limit.These values can be convenient by using standard Calorimetric Techniques (such as DSC (differential scanning calorimetry)
Measurement is measured with 20 DEG C/min.
In general, biggish Δ Tsc is related to lower critical cooling rate, although the scattering (scatter) of significant quantity exists
Δ Tsc value greater than 40 DEG C exists.With being greater than 40 DEG C of Δ Tsc, and preferably greater than 60 DEG C, and still more preferable 70 DEG C or more
The bulk-solidifying amorphous of high Δ Tsc be it is very desired, this is because being relatively easy to be formed.In supercooling liquid phase region,
Bulk-solidification alloy acts like high-viscosity fluid.The viscosity of bulk-solidification alloy with wide supercooling liquid phase region from
1012Pas (in glass transition temperature) drops to 107Pas and drop to 10 in some cases5Pa·s.Heat block
Solidified superalloy to be more than crystallization temperature cause crystallization and alloy excellent properties loss immediately and its cannot re-form.
The superplasticforming (SPF) of amorphous metal alloy includes being heated to SCLR and making under an applied pressure
It is shaped.This method be similar to thermoplastic material processing, wherein the formability being inversely proportional with viscosity as the temperature increases and
Increase.However, with thermoplastic material on the contrary, high viscosity amorphous metal alloy is metastable and finally crystallizes.
Due to several, it is necessary to avoid the crystallization of amorphous metal alloy.Firstly, which reduce amorphous metal alloys
Mechanical performance.From the perspective of processing, crystallization limits the process time of thermoforming operations, this is because in crystalline material
In flowing it is higher than the order of magnitude of the flowing in liquid amorphous metal alloy.The crystallization of various amorphous metal alloys is dynamic
Mechanics makes process time in the range of viscosities between minute and hour.This becomes super plastic forming method can be
The method fine-tuned that convenient time specification carries out, makes it possible the net forming of complex geometry.
The ability for thermoplasticity forming amorphous metal alloy is described by its formability, and formability is directly related to
The parameter to interact between temperature dependent viscosity and crystallization time.During the TPF of amorphous metal alloy, it is necessary to
It avoids crystallizing, because it makes amorphous metal alloy property-deterioration and slows down its formability.Therefore, it is closed in amorphous metal
The time passed during the TPF of gold must be shorter than crystallization time.
Sheet (as final products or as the raw material for further processing) is one of the most important shape of metal.
Particularly, for glassy metal, sheet is high expectations, because they are thin in one dimension, and such
In geometry, block metal glass (BMG) often shows bend ductility.For example, having shown that with a thickness of~1mm's
The BMG of medium range shows bend ductility.
However, BMG sheet material, the manufacture of especially big BMG sheet material is challenging always, and the prior art is not opened up also
The sheet material that size is more than about 10cmx10cm is shown.
Conventional casting is not particularly suited for the manufacture of the BMG sheet material manufactured by rolling method, because this method needs lance
The requirement-of shield is quickly cooled down on the one hand to avoid crystallization with Slow cooling on the other hand to fill entire mold cavity.It is double
Roller casting must carry out in high vacuum or protective atmosphere, and challenging control problem.The cold rolling of BMG is very
Limited, because BMG is plastically deformed by forming shear band at room temperature high localizedly, wherein the overwhelming majority answers changed situation
Portion, different from uniform deformation needed for rolling.Therefore, the deformation realized during cold rolling be it is highly non-uniform,
And it is more than about the raw material of 1mm for thickness, causes directly to rupture.
At a temperature of (T in the supercooling liquid phase region of specific BMGg<T<Tx) deformation be also explored for shaping and adding
Work.In supercooling liquid phase region at a temperature of, for actual strain rate, BMG is in low stress ,~1/100 room-temperature yield strength
Lower homogeneous deformation, and so low utilizing for flow stress has been explored for manufacturing thin BMG disk.
Trial has been made with the rolling BMG in supercooling liquid phase region.Most successful is wherein to be heated by heating plate
Method, which passes through roller together with raw material.However, permanently connecing in this BMG with clamping and thereby heat the heating plate of BMG
Touching.Therefore, the principal benefits (reduction of the contact area between mold (roller) and material) of rolling sacrifice, and deforming is phase
When limited.It is about 7cmx5cm by the maximum and most thin block (piece) that this method obtains, with a thickness of about 0.4mm.Due to
Raw material and mold (heating plate) are permanent contacts, also can not be achieved big thin sheet material with the technology.
Thermoplastic molding is processed, wherein BMG and mold permanent contact, for constant pressure, the increase of radius and when
Between ^1/8It is proportional.Therefore or unpractiaca long-time (far more than crystallization time, which defines maximum process times) is with reality
Existing large radius is necessary or needs impractically high pressure.Therefore, wherein the technology discomfort that entire BMG is contacted with mold
Share the BMG sheet material big and thin in manufacture.
The U.S. Patent number 8 of Prest et al., 485,245, theme passes through reference herein and is incorporated in its entirety, describes
Melting BMG alloy is poured onto the molten metal with more higher than BMG melt density and lower temperature in float chamber
Method in bath to disperse and solidify BMG melt and form BMG sheet material.The technique depends on the solidification of BMG melt.
However, it is difficult to thickness be controlled, this is because resulting balance sheet thickness is the gravity by BMG melt and molten bath
It is limited with surface tension.In addition, inert gas environment and/or vacuum are needed in molten alloy room and float chamber.
The U.S. Patent Publication No. 2013/0025746 of Hofmann et al., theme pass through reference in its entirety simultaneously herein
Enter, describes the method that BMG sheet material is manufactured by the twin roller casting of BMG melt in inert environments.This method includes that will melt
BMG melt injection enter chilling roller in so that metal glass melt is frozen into sheet material.As additional selection, the BMG piece that leaves
Material further can form thinner sheet material by one group of subsequent roller thermoplasticity.
In the process, such as get off to process BMG melt: first by chilling roller to be used for solidified cast, and after then passing through
One group of continuous hot-rolling is to be used for hot rolling.The twin roller casting method make BMG melt be frozen into sheet material and must in a vacuum or
It is completed in inert environments.In addition, not being desired by the thickness of the BMG sheet material of twin roller casting, because it is often non-equal
Even, there is the typical thickness less than about 200 μm.After twin roller casting, also needed by subsequent one group of roller thermoplasticity rolling
Very high rolling stress is wanted further deform fine sheet and obtain thinner sheet material.
The U.S. Patent Publication No. 2014/0064043 of Tsuchiya et al., theme pass through reference in its entirety simultaneously herein
Enter, describes the method for manufacture clock spring, by the way that BMG melt list roller is cast as sheet material, then superplasticity rolling BMG piece
Material is to eliminate the aperture cast on caused BMG clock spring surface.
Similar to Hofmann, technique is carried out from chilling roller to hot-rolling and dependent on solidification of the BMG melt in inert environments.
It is small in BMG sheet surface when this causes to solidify in the state that wherein air is maintained on the surface of BMG or in inside as BMG
Hole.Thickness is also uncontrollable (that is, be heterogeneous and usually less than about 200 μm).The hot rolling step of superplasticity only designs
For for keeping the surface of BMG sheet material smooth；It cannot be such that sheet material deforms, due to high hydrostatic stress shape during hot rolling
State.Finally, do not apply uniaxial thermoplasticity to stretch.
The U.S. Patent Publication No. US of the U.S. Patent number 8,613,814 of Kaltenboeck et al. and Johnson et al.
2014/0047888, respective theme passes through reference herein and is incorporated in its entirety, describes using quick in several milliseconds
The method that capacitor discharge technology quickly heats and forges block metal glass.Although this method can quickly soften BMG,
But the pyroplastic deformation or forging stress for this method are very high, this is because the Large strain in short time scale
Rate and the high hydrostatic stress under casting, therefore limit it and be used to manufacture big BMG sheet material.
Therefore, in this field exist under actual condition (for example, in air and under practicable pressure) with
Controlled mode can be such that glassy metal deforms to produce the method for the block metal glass sheet material with any thickness and size
Demand.In addition, in the presence of the demand for the manufacturing method that can produce big, thin block metal glass sheet material in this field.
Summary of the invention
The object of the invention is to produce block metal glass sheet materials.
It is another object of the present invention to manufacture the block metal glass sheet material with uniform thickness.
It is another object of the present invention to agglomerate body glassy metal sheet material is manufactured under advantageous processing conditions.
It is of the invention still another object is that manufacture has the block metal glass sheet material of complex pattern.
It is of the invention still another object is that manufacture block metal glass web.
It is of the invention still another object is that passing through hot rolling engagement block glassy metal sheet material or web.
It is of the invention still another object is that system for manufacturing block metal glass sheet material and web.
For this purpose, in one embodiment, it, should the present invention relates generally to manufacture the method for block metal glass sheet material
Method the following steps are included:
A) preheating block metal glass raw material does not provide to being enough to soften block metal glass raw material but significantly block
The temperature of the crystallization time of the consumption of body glassy metal；With
B) between one group of heating roller of the processing temperature for being maintained at block metal glass thermoplasticity rolling through preheating
Block metal glass raw material；
Reduce the thickness of block metal glass raw material wherein to produce block metal glass sheet material.
The present invention is also generally related to the system for manufacturing block metal glass sheet material, which includes:
A) one group of pre-add hot plate, wherein this group of pre-add hot plate can clamp block metal glass raw material therebetween to preheat
Block metal glass raw material is to being enough to soften block metal glass raw material but does not provide the consumption of block metal glass significantly
Crystallization time temperature；
B) it is maintained at one group of rotary heating roller of the processing temperature of block metal glass, wherein when this group of heating roller rotates
When, the heating roller thermoplasticity rolling from pre-add hot plate the step of receive block metal glass raw material therebetween so that block is golden
It is thinning at block metal glass sheet material to belong to glass raw material；With
C) drawing mechanism can pull down in controlled velocity and extend away from the block metal glass through rolling of this group of heating roller
Sheet material.
Brief description
For a more complete understanding of the present invention, with reference to following explanation relevant to attached drawing, in which:
Figure 1A, 1B, 1C and 1D depict a variety of methods for keeping glassy metal thinning in their subcooled liquid state.
Fig. 2 depicts the two methods of BMG processing technology.
Fig. 3 A and 3B illustrate the relationship between formability and processing temperature.
Fig. 4 A and 4B depict maximum change of the preheating to may be implemented during hot rolling with insignificant drawing force
The effect of shape.
Fig. 5 depicts single step (routine) processing scheme together with the temperature curve of processing scheme of the invention.
Fig. 6 depicts Zr44Ti11Cu10Ni10Be25The TTT diagram of BMG.
Fig. 7 depicts the Zr through rolling44Ti11Cu10Ni10Be25The full-size of BMG sheet material.
Fig. 8 depicts schematic diagram of the rolling system in conjunction with drawing process.
Fig. 9 depicts the comparison of rolling force and drawing force for identical speed (3mm/s).
Figure 10 is depicted under thermoplasticity rolling as the maximum shear stress of the function of sheet thickness and maximum hydrostatic pressing
The comparison of power.
Figure 11 A depicts the Zr of institute's rolling44Ti11Cu10Ni10Be25BMG sheet material and Figure 11 B, which are depicted, is removing Surface Oxygen
Zr after change44Ti11Cu10Ni10Be25BMG sheet material.
Figure 12 depicts the rolling installation according to the present invention for BMG material.
Figure 13 depicts the exploded view of the key component of rolling device according to the present invention.
Figure 14 depicts the example of pre-add hot plate according to the present invention.
Figure 15 depicts the Pd of institute's rolling43Ni10Cu27P20Sample.
Figure 16 depicts the example for manufacturing pattern (in plane or outside plane) in BMG sheet material using patterned rolls.
Figure 17 depicts the example that pattern is manufactured in BMG sheet material using thermoplastic extrusion molding or blow molding method.
Figure 18 depicts the example of the patterned spectacle frame in the BMG sheet material processed according to the present invention.
Figure 19 depicts the sandwich of rolling block metal glass raw material with complete (a) or part (b) grafting material
Sandwich and deform the sandwich of material.
Equally, all with identical reference numerals although not every element can make marks in each figure
Element indicates component similar or identical.
The specific descriptions of preferred embodiment
The present invention relates generally to deform glassy metal to manufacture large area bulk metal under the conditions of low power and stabilisation
The method and apparatus of glass sheet and block metal glass item and band." sheet material " refers to wide extension or block metal glass
Surface." web " or " band " refers to growing one piece of narrow block metal glass.In both cases, block metal glass piece
Material or web are through manufacturing the thickness to have less than about 1mm.
As described previously for the prior art based on thermoplasticity rolling, roller is usually cold (~room temperature), this is than desired
Rolling temperature is much lower.Therefore, after rolling, BMG is cooling and its flow stress quicklys increase.Critical aspects of the invention are
Opposite-BMG material temperature when close to roller is established to increase and consider that the consumption of the formability before contacting roller optimizes
Its increased amount.The viscosity of time needed for this minimum reaches rolling temperature and optimization during rolling is big to allow
Deformation, make separation and laminar flow be achieved.
Surprisingly it has been found that be difficult by using the BMG sheet material that only hot rolling obtains great Bao, this be by
(wherein η is viscosity to the hydrostatic pressure needed for reaching actual shearing deformation, and U is rolling speed, and R and h are roller and sheet thickness
Radius).Hydrostatic pressure can be considered as losing, this is because the shear-deformable gradient for being only dependent upon pressure；Most of folder
Only hydrostatic squeezes BMG without any permanent deformation to clamp force.Common size and thickness are reduced, hydrostatic pressure consumes
The power that the overwhelming majority is applied and the producible pressure of clamping force more than the hot rolling mill as obtained by reality.Letter speech
It, it is the BMG sheet material that 20cmx20cm and thickness are less than about 0.05cm that thermoplasticity rolling itself, which does not allow for manufacture oversize,
It is lower than 10 even for viscosity obtained by those considerably less minimum reality7The glassy metal of Pas is also such.
Present inventors have found that the stretcher strain of BMG is that deformation force is (wherein essentially all of to be applied
Power be used to deform) the result effectively used.However, being observed unstability (constriction), especially when stretching is used only
Under high tensile speed.Therefore, thickness change is unacceptably high and is deteriorated because of multi-pass processing as shown in Figure 1A.
However, when one or more hot rolling and drawing are combined along negative temperature gradient under controlled speed (not being power)
When stretching, the power for deforming block metal glass can be strongly reduced, and can get big, thin sheet material.In addition, the combination cause it is high
Stability, and the very small thickness change of the sheet material through manufacturing.
It is known to be quickly cooled down the mechanical performance that will affect BMG.However the deformation that do not reported also in process of setting can also
Influence mechanical performance.The inventors found that sample deformations are until its solidification using method described herein.In addition, right
In in process of setting the sample of drawn measured bend ductility more higher than unstretched sample.
The present invention relates generally to the method and systems for manufacturing the glassy metal sheet material with controlled dimensions.Glassy metal
It is deformed under the conditions of manufacturing the low power of thin and large-area metal glass sheet and stabilizing.The present invention have production it is both big (for example,
At least 20cmx40cm depends on specific BMG) and thin (that is, thickness is less than about 1mm, preferably less than about 0.5mm, it is most preferably small
It is thin in about 0.1mm, and even more, the ability of the glassy metal sheet material depending on specific BMG).
The present invention is based on thermoplasticity rolling technology, optionally, it is preferred that combining with stretcher strain.It is based on one
Kind or a variety of thermoplasticity rollings and the combination for stretching and (being combined with preheating method).The Main Patterns of deformation depend on BMG item
Part such as thickness, viscosity and crystallization time.Method described herein avoid sheet material (it is especially further described below by
Big and thin sheet material made of BMG with low formation) it crystallizes in manufacturing process.By preheating, reduce consumed
Process time can be used, this allows using thick raw material.Deformation be used to reduce thickness to lower than us during hot rolling
The only very limited deformation relied on；Minimum requirements is the mitigation disturbance in terms of thickness.
Therefore, in one embodiment, the present invention relates generally to manufacture the method for block metal glass sheet material, this method
The following steps are included:
A) preheating block metal glass raw material is to being enough to soften block metal glass raw material but not significant offer block
The temperature of the crystallization time of the consumption of body glassy metal；With
B) between one group of heating roller of the processing temperature for being maintained at block metal glass thermoplasticity rolling through preheating
Block metal glass raw material；
Reduce the thickness of block metal glass raw material wherein to produce block metal glass sheet material.
In the first procedure of processing, glassy metal is heated to 0.8Tg<TPreheating<1.4Tg(Tg: it is heated with 20K/min
Glass transition temperature in the process, by DEG C in terms of) temperature with pre-add hot charge BMG for subsequent rolling step.This is pre-
Heating time needed for heating step reduces rolling has simultaneously softened BMG, this leads to effective heat transfer between roller and BMG raw material,
And thus quickly heat up to 0.7TX<TProcessing<1.3TX(Tx: with the crystallization temperature in 20K/min heating process, by DEG C in terms of) roller
Temperature.If sheet material has been thin, such as after several passages, when thickness be lower than 1mm when, the preheating steps become compared with
Not effectively (or can even be skipped).Then, BMG raw material is in 0.7TX<TProcessing<1.3TXThe hot rolling of temperature.
Hot rolling be used to keep raw material thinning, but work asBecome non-when (mainly for fine sheet)
Often not effectively, wherein R is the radius of roller, and Δ h and h are thickness reduction and film thickness respectively, since hydrostatic pressure is in lubrication near field
Increase very fast.In general, rolling force is to the contribution of plastic deformation less than 10% in that region.However, hot rolling is another
One benefit be can reduce it is any cause " necking down " instable disturbance (original depth variation), this helps to stabilize subsequent
Drawing process.
After block metal glass sheet material leaves from this group of heating roller, block metal glass sheet material optionally it is preferred that
It is exposed to drawing force.Surprisingly, the drawing force is usually than the hot rolling of glassy metal to realize needed for identical deformation rate
Clamping force it is much smaller.Drawing force is applied into entire temperature gradient and block metal glass sheet material is moved along temperature gradient.
This stabilizes processing and prevents instable generation during related thinning.
It stabilizes one stretched and requires to be the condition for occurring under conditions of being stretching in speed control, rather than controlling in power
Lower generation.Therefore, all drawing forces are used for stretcher strain, and similar deformation rate is realized during hot rolling,
Very big hydrostatic pressure must be applied.Do not make raw material thinning for the power that establishment hydrostatic pressure is applied and can be considered as damaging
It loses.Therefore, drawing force is especially thin in wherein BMG raw material significantly less than the clamping force applied in hot rolling process
Later phases.
Therefore, the BMG sheet material of Bao He great can be realized by combined rolling as described herein and drawing process.Therefore, it deforms
The more effective BMG alloy using with much broader range of power is (that is, even have up to 1010Pas is (practical to can be achieved
Those of) minimal viscosity) sheet material can be formed, this is by being impossible based on thermoplastic rolling.
Surprisingly it has been found that deformation passes through the free body by raising bulk modulus to the ratio generation of modulus of shearing
Long-pending or equivalent amount also influences the mechanical performance of BMG.If solidification during stretching causes to be only more prolonging for hot rolling than BMG
The BMG of malleability.Therefore, method described herein can produce the BMG with increased ductility, even if in common processing conditions
In the process, they also can be brittle.It can be by 0.8mm Zr for example, it was discovered that stretching rolling44Ti11Cu10Ni10Be25Bulk metal
The bend ductility of the band of glassy alloy increaseds to over 3% from less than 2%.
Such method, which is realized, minimizes formability consumption before raw material contacts roller, and in stabilisation and for by heat
Keep required distortional stress minimum by the stretching of speed control in the temperature gradient of the thicker raw material of rotary rolling mill step auxiliary
Change.
Figure 1A, 1B, 1C and 1D, which are depicted, to be kept glassy metal thinning in their subcooled liquid state and wherein stretches
The a variety of methods realized by speed control (rather than power control).Figure 1A (situation 1) illustrates the constant drawing in uniform temperature
It stretches, leads to whole necking down and the non-uniform thickness of raw material.Figure 1B (situation 2) is illustrated using only the temperature gradient field stretched.Such as
Shown in Figure 1B, in the drawing process not along the hot rolling of temperature gradient, the typical of surface defect on BMG raw material is deposited
Serving as " disturbance ".These disturbance sustainable growths during stretching, lead to localized necking behavior.Fig. 1 C (situation 3) explanation
By the hot rolling not stretched along temperature gradient, can produce it is very limited strain so that BMG raw material deforms, this be because
For hydrostatic pressure very high in hot rolling.Finally, Fig. 1 D (situation 4) is illustrated by merging hot rolling and stretching, disturbance
It can be substantially eliminated and may be implemented the pyroplastic deformation of much higher strain and stable state.
Fig. 2 depicts the two methods of BMG processing technology.Path 1 is to rely on the quick quenching of liquid melt with shape
At the liquid cast technique of BMG, and path 2 depends on the thermoplastic forming of the BMG in subcooled liquid state.
For manufacturing the prior art of the BMG sheet material based on liquid condition processing, such as twin roller casting, single roller casting, note
It penetrates molding or topples over melted melt in balneation, all the processing method of passage path 1 carries out.As described above, there are several in path 1
Major defect, such as very high temperature (being higher than fluid temperature), are quickly cooled down to avoid crystallization (narrow process window), to height
The demand of vacuum or inert atmosphere, the control being very limited.
On the contrary, for manufacture the processing method based on path 2 BMG sheet material there are many advantages, including much lower temperature
Degree and bigger process window.In addition, in air carry out 2 processing technology of path be also possible to it is feasible.
The ability of BMG is processed to thermoplasticity in temperature dependency formabilityMiddle quantization.Such as Fig. 3 A and 3B institute
Show, formability increases with the increase of processing temperature.The behavior is surprising and to appear in BMG be generally existing
's.Large-scale BMG is had studied, some of which is summarised in Pitt, E.B., G.Kumar and J.Schroers,
Temperature dependence of the thermoplastic formability in bulk metallic
Glasses.Journal of Applied Physics, (2011) 110 (4).
The behavior has indicated the processing side of the practical manufacture as described herein for big, high-quality and thin sheet material
Case.Therefore, in thermoplasticity make in glassy metal deformation process, in order to maximize deformation, high temperature is selected, in Fig. 3 A
Shown, the formability which depict glassy metal is the function of crystallization time and viscosity, and both of which is the strong of temperature
(strong) function.Surprisingly, for all considered BMG, formability increases with the increase of processing temperature.So
And with increased temperature, crystallization time reduces.Therefore, the sheet material big for rolling, it is necessary to make efforts to obtain high temperature
Degree, while avoiding crystallizing.Experimentally realize that the shapable state of the height may be very challenging.
In order to solve this problem, present invention uses the processing schemes for optimizing pre- rolling conditions.Formability is low, and
BMG raw material, which sufficiently softens, enables to quickly heat up to rolling temperature (that is, processing temperature in specific range of temperatures) simultaneously
And also optionally, but it is preferable to use stretcher strain is as primary deformable technique.Stretcher strain is needed than in hot rolling process
The much lower power of middle deformation, and therefore can be deformed in lower temperature and retain formability.
The preheating of BMG raw material is effective first procedure of processing of methods described herein, causes to pass through the prior art
Technique obtained by whole bigger possibility deformation.Preheating to during hot rolling with insignificant stretching rolling force
The effect of (lateral sheets of sizes) achievable maximum distortion is illustrated schematically in Fig. 4 A and 4B.
Fig. 4 A depicts achievable maximum distortion during hot rolling in any preheating of no use.
As shown in Figure 4 A, in no preheating, BMG raw material is only to be slowly heated to desired rolling temperature, this makes
At the slow deformation of BMG raw material, while consuming formability.
On the contrary, as shown in Figure 4 B, when BMG raw material is from TPreheatingIt is preheated to TRollingWhen, there are the faster deformation of BMG, this
Formability is remained, and to manufacture big, thin BMG sheet material.Preheating steps fully soften BMG so that
The close contact of roller formation and BMG is obtained, therefore heats BMG more quickly.
For the BMG with highest formability, technical staff can actually realize rolling operation~f=10-4Pa-1.This is right
Ying Yu is 106About 1 minute process time of the viscosity of Pas.In typical thermoplasticity processing scheme, heats the raw material to and add
Work temperature.The processing consumption about 1 minute, however, only only a part facilitates the consumption of formability, as shown in Figure 5.This
It is close to the temperature region of setting temperature, TSetting± 10%.Must be taken into consideration it is only a fraction of the reason is that because crystallization time with
Temperature increase and rapid decrease, and when close to setting temperature when the rate of heat addition decline.The rate of heat addition and material temperature and
The difference that temperature is arranged is proportional.On the contrary, in the present invention, instead of to directly heat to ideal rolling temperature, first by BMG original
Material is substantially preheated to lower temperature.It is longer in this crystallization time, and the formability of significant more fraction is therefore consumed, such as
Shown in Fig. 3 A and 3B.
As shown in figure 5, the consumption of formability can sharply subtract during heating due to for 2 step process in the present invention
It is small.During current, when close to TPreheatingThe rate of heat addition declines when (having the consumption of insignificant formability), and wherein
Since different heating mechanisms is (from TPreheatingTo TRolling) consume significant formability temperature region increase.
Present invention utilizes the exponential dependences of crystallization time and temperature.Raw material BMG, which is heated to wherein crystallization time, is
It is very long (that is, in Tg, crystallization time is about one day or longer) and temperature.However, the temperature is close from the viewpoint of heat
In processing temperature.Therefore, the temperature of preheated raw material increases by tens degree only necessarily through this group of heating roller and is added with realizing
Work temperature can be by feeding preheated raw material BMG by this group of heating roller come real with heating quickly and precisely to increase
It is existing.Then, cooling can be realized by the free convection of processing environment or can be by the way that gas or liquid are forced at the piece left
Enhance on material.Therefore, the use of preheating steps leads to only small overall deformation and can also cause the damage to roller.Cause
This, is preheated to such temperature for block metal glass, and wherein the temperature can compared with its pot life in processing temperature
To keep long period, it is preferably at least 10 times long in one embodiment to 5 times of the youthful and the elderly.In other words, by bulk metal
Glass raw material, which is preheated to, is enough to soften block metal glass raw material but the consumption of not facilitating block metal glass significantly
The temperature of crystallization time.Meanwhile in terms of heat, the pre-heating temperature is close to rolling temperature, and BMG raw material has filled
Divide softening, so that it is deformed in which can be easy thermoplastic.
Fig. 6 illustrates Zr44Ti11Cu10Ni10Be25The TTT diagram of BMG.As shown in Fig. 6, crystallization time with
Temperature increase and rapid decrease.
Fig. 7 illustrates Zr of the maximum through rolling in different temperatures44Ti11Cu10Ni10Be25BMG sheet material.Initial feed is complete
Portion is all the disk of 1.7mm thickness, 14mm diameter.Indicate the number of passage before crystallization.As shown in Figure 7, it uses
Zr44Ti11Cu10Ni10Be25BMG is optimal process temperature that define 440 DEG C, to generate possibility from the perspective of rolling
Highest thickness reduce and possible most thin sample.
In general, rolling is with the progress of several passages, range can be 3-15 passage.At 440 DEG C,
Zr44Ti11Cu10Ni10Be25BMG shows 5-6 minutes before crystallization process windows.In a step heating process, at 440 DEG C
For being consumed~25 seconds in total 5-6 minute per pass.Actual rolling (raw material is contacted with roller) depends on such as sheet material
Length, roller radius, rolling speed and for common BMG rolling, practical rolling has spent about 10 seconds.Therefore, via 10 passages
Rolling consumes about 6 minutes process times, it is meant that BMG sample can have begun crystallization.Before BMG sample crystallization, most
It is big to be therefore only about 9 passages.If having selected nonideal low processing temperature, such as 420 DEG C, 8 minutes process times were can
It obtains, and therefore can carry out being greater than 10 passages before sample crystallization.However, the deformation realized is low because this compared with
The viscosity dramatically increased under low temperature.Other temperature are also depicted in Fig. 7.
In the present invention, pre-heating temperature is made to optimize supreme but be sufficiently low so that significant provide does not disappear
The temperature of the crystallization time of consumption.The temperature is close to processing/rolling temperature so that temperature can be improved rapidly to processing temperature.
The reason of rapid heating capability, is as follows in the procedure of processing:
(1) temperature is already close to processing temperature, usually > TRollingAbout 20% to about 35%, more preferably from about 30%；With
(2) flexibility of the BMG raw material of preheated state causes and entirely contacts pipeline intimate contact, and therefore can realize
Quick heat transfer.
For example, crystallization occurs after 35 minutes if BMG is in 390 DEG C of preheatings, rollings, and then in 440 DEG C of rollings, this
It is more much longer than the crystallization time specification in 440 DEG C of (without preheating steps) 5-6min.Therefore, formability during heating
Consumption is strongly reduced to pre-heating temperature and can be consumed during rolling step.Therefore, processed with a step~10
Secondary to compare, by using method described herein, BMG raw material can be up to~16 passages before crystallization with rolling.
As described herein, only just find that the power reached needed for desired thickness reduces is significant by thermoplasticity rolling
High, for sheet size (that is, wherein out-of-plane size is than much smaller size in plane).However, if
Addition stretching step as shown in Figure 8, then due to drawing force, F can further subtract the thickness of sheet material after leaving from first group of roller
It is small.
Drawing force can be applied by a variety of methods, including for example by (1) second to " cold " roller (that is, be maintained at than heating
The lower temperature of the processing temperature of roller), drawing force is rotated to produce with than the first group higher speed of heating roller；Or (2) are logical
Cross the draw-off mechanism of speed control.Drawing force is applied to bulk metal glass when block metal glass leaves first group of heating roller
Other methods of glass can be also known to the skilled in the art.For stretching crucially controlled velocity and negative temperature gradient two
Person.
Drawing force is calculated according to σ=F/ (h*W), and wherein W is the width of sheet material.The stress of tensile part is directly proportional to 1/h.
This means that the thickness with the sheet material through rolling declines, driving stress be will increase until sheet material is broken.Surprisingly however it was
It was found that raw thickness variation can reduce so that even some thickness disturbances can be endured before the stretching, without BMG with not
Stable mode increases.
Keep the requirement for the combinative stability for squeezing and stretching rolling as follows:
(1) when BMG sheet material leaves first group of heating roller, negative temperature gradient.To, with from first group of heating roller away from
From increase, viscosity increases, and therefore deformation resistance increases；
(2) it stretches through and accurately controls displacement to realize.In other words, stretching is speed control, rather than power controls
's.Usual viscosity is at least substantially constant；With
(3) variation of the thickness occurred during stretching can be planarized by subsequent rolling passage.
Fig. 8 illustrates the schematic diagram of the rolling system in conjunction with drawing process, wherein second group of " cold " roller be used to control
The stretching of sheet material through rolling is so that it is thinner.
The deformation mechanism of thermoplasticity rolling and stretching is different.For thermoplasticity rolling, thickness reduces from shearing
Deformation (is similar to and squeezes flowing), and for stretching, thickness reduces from stretcher strain.
In order to quantify the preferred deformation pattern for different BMG processing conditions (such as thickness, viscosity and crystallization time),
Thermoplasticity rolling and drawing force can be calculated.
In calculating below, problem is reduced to 2D problem, that is, assuming that the thickness of sheet material is small enough to than the other of it
It is more, and the BMG for deforming in supercooling liquid phase region, BMG are considered as not squeezable Newtonian fluid.Reynolds numberIt is actually much smaller than 1, and therefore body force (body force) such as gravity and Inertia can be neglected
Slightly.
Based on this, the pressure in rolling, which can be used, to be determined as shown in equation (1) without slip boundary condition:
Wherein η is viscosity, and U is rolling speed, and x is along rolling direction, hm、R、h1It is the gap between roller respectively, the half of roller
Diameter and sheet thickness in outlet.
Then rolling force can be calculated according to equation (2):
Drawing force is estimated according to equation (3):
Wherein w is sheet width, and Δ U is the speed difference and L between two ends of sheet material0It is length, occurs wherein
Thickness reduction.
In order to compare rolling and drawing force, Δ h/h0=40% thickness reduction is used as example and assumes that roller gap is just
The half of beginning sheet thickness, w=10cm, η=106Pas, U=3mm/s, Δ U=U and L0=lcm, this is for practical control
Reasonably, for example, it is desired to make high-temperature cooling so that stabilization.In one embodiment, in deformation period institute
The difference of the deformation force of the identical deformation realized, thermoplasticity rolling and stretching is at least 10 times.
As a result shown in Figure 9, the rolling force and drawing force of identical speed (3mm/s) are compared, wherein thickness reduces Δ
h/h0=40%, roller gap is the half of initial sheet thickness, sheet material=10 cm and viscosity=106Pa·s.It is very astonishing
Ground, power needed for reaching identical speed and thickness reduction speed during stretching are substantially less than in rolling process.Therefore, it is
Realize the sheet material of 0.5mm thickness, about 1,000 times of rolling force up to drawing force.
Based on equation (3), it is apparent that all drawing forces be used to be plastically deformed, and for thermoplasticity rolling, shearing
Stress rather than hydrostatic pressure promote to be plastically deformed.The function as thickness is compared for rolling parameter identical in Fig. 9
The maximum shear stress and maximum hydrostatic pressure, as shown in Figure 10.As shown in Figure 10, maximum quiet as sheet thickness reduces
Water pressure significantly quicklys increase.In addition, maximum hydrostatic pressure is often more much bigger than the maximum shear stress, it means that pass through thermoplastic
Property rolling manufacture thin sheet material with sheet material is thinning and become more and more not effectively.15.
Principal benefits of the invention first is that its permission manufactures sheet material in ambiance.On the contrary, being proposed before most of
For manufacturing the alternative method of sheet BMG component, including method is for example cast, and twin roller casting and alloy melt forming need
Vacuum or inert gas or reducing environment are wanted, this is unpractiaca in a manufacturing environment.It is apparent that overwhelming majority BMG is suggesting
Temperature and processing conditions in aoxidize.However, surprisingly discovery oxidation is surface and the surface for being limited to sheet material.
Oxide layer exists only in surface crown (thin) depth (1-2 μm).Figure 11 A illustrates institute's rolling with thickness~450 μm
Zr44Ti11Cu10Ni10Be25BMG sheet material (TRolling- 440 DEG C, TPreheating=420 DEG C, 13 passages).Figure 11 B illustrates removing 1-2
Identical BMG sheet material after micron surface.
However inventor has found that the surface that oxide is limited to BMG sheet material is desirable for laminar flow.Therefore, of the invention
It is limited to lead to laminar flow and avoids the processing conditions of turbulent flow.The condition of such flowing can be limited by Reynolds number, wherein
Need the Reynolds number significantly less than 1 to form laminar flow.For technique for rolling, Reynolds number can be calculated asWherein
ρ, η and h are the density, viscosity and thickness of raw material respectively, and U is rolling speed.Laminar flow of the present invention requires to include following item
Part: being the rolling thickness of 10 μm of -20mm respectively；Viscosity: 103-1010Pas, density: 3-20g/cm3；Rolling speed: 1-
200cm/min, all generation Re ≈ 10-13-10-3<<1。
The BMG that can be processed according to the present invention can formally be divided into four groups, even if they fall in the non-individual body as shown in table 1
(continuum) in.
The type of table 1.BMG
The demand of stretching depends in part on the BMG of concrete type and the desired size of finished product BMG sheet material.
BMG with excellent formability is in TxShow 106The viscosity of Pas.Their formability is greater than or equal to 10- 4Pa-1.It preheats and is still needed during the initial stage of rolling thickness raw material (> 3mm).Frequently, for the BMG class
Type, processing temperature can be selected as lower and therefore biggish process time is obtainable and crystallization can more easily be kept away
Exempt from.It stretches and is needed only for big sheet material (that is, having greater than about 40cm multiplied by the size of about 20cm).
BMG with high formability is in TxShow 106~107Pas or smaller viscosity.Their formability is about
10-4~10-5.It preheats and is still needed during the initial stage of rolling thickness raw material (> 3mm).It stretches for big sum
Medium sheet material (that is, having greater than about 20cm multiplied by the size of about 10cm) is needed.
BMG alloy with medium formability needs to stretch for most geometries.With the clamping force of 30kN, this
A little achievable final sizes of alloy differ markedly from high formability BMG.Big sheet material can only be realized by stretching.Use this
Technology described in text, having about 20cm multiplied by the BMG sheet material of about 10cm size is possible.
BMG alloy with low formation is in TxWith greater than 109Pa·s(F<10-6Pa-1) viscosity have low formation
And it is deformed during rolling not significant.Therefore, most deformations must occur during stretching.When including stretching
When, preformed thin plate still can be thinning.Using the techniques described herein, with about 20cm multiplied by the BMG piece of the size of about 3cm
Material is possible.
However, have in all wherein BMG raw materials > thickness of 3mm in the case where, preheating raw material before rolling is
It is necessary.For raw materials size, for example, wherein raw material is that have thickness < 1mm sheet after several passages, pass through roller
Heating can become sufficient and no longer need to preheat.
Another critical aspects of the invention are accurate temperature and process time control.Accurate temperature control can pass through control
The temperature of heating element processed is realized.Group heating is placed in this group of heating roller and is used to control for example, thermocouple can be fed back
The temperature of cartridge heater in roller.In alternatives, temperature control can also be by using the radiant heat on the outside of this group of heating roller
To realize.Roller can also be heated by submerging in the liquid of heating.Accurate temperature controlled other temperature are allowed to control dress
It sets and is also known to the skilled in the art and can be used for the present invention.
As shown in figs. 12, in one embodiment, roller is with the resistance heater by PID- control control
Heating, wherein thermocouple (surface for being positioned proximate to roller) be used to measure temperature.It is highly desirable that in roller surface
Temperature uniformity in entire roller large deviations less than 5 degrees Celsius.
As described above, preheater is key element of the invention, because which reduce the consumption of the formability of BMG.Preheater
Requirement be that BMG raw material sufficiently softens so that BMG does not damage roller, adapt to the shape of roller, and make formability consumption minimum simultaneously
Change.
In one embodiment, as shown in Figure 12, preheater may include heating when raw material passes through preheating steps
Two heating plates (top and bottom) of raw material.Temperature control is crucial in preheating process, however there is no rolling
It is crucial like that during rolling.Preheater is optionally but it is preferred to have heating and control mechanism independently of roller.Heating and control
The technology of preheater processed can be similar to the technology for being directed to roller suggestion.
Preheater shown in Figure 12 allows temperature to control in ± 5 degrees Celsius.In an embodiment of the present invention, two
Heating plate is simply by gravity extruding raw material.However, specific BMG type is depended on, and the BMG in the type
The geometry of specific property and BMG raw material, can add additional power.Such power can be adjusted to as needed it is higher or
It is lower.
With lateral sheets of sizes is increased, the tendency that BMG is adhered on roller can be problematic.It is viscous must to solve BMG
It is attached to roller, to keep flatness, thermal conductivity, and continuous formability during entire rotary rolling mill.Raw material adheres to roller
On tendency can by comparing adherency driving force (due to due to reduced system energy of adhesiveness) and resistance (due to
Due to curved increased strain energy) quantization.For Newtonian fluid, since the increased bending energy of adhesiveness is shown in equation (4)
In:
Wherein the η of λ=3 is tension (tension) viscosity of sheet material, and Ω is the angular speed and I=h of roller2 3/ 12 be cross section
Rotary inertia.
On the other hand, the adhesion energy of system is shown in equation (5):
Us=(γs-v-γs-l) s=(γs-v-γs-l) R θ=γl-v cosβ·Rθ (5)
Wherein β is the contact angle between glassy metal and roller.
Therefore, in order to prevent adherency during rolling, it is desirable that:
Or
Adherency tendency does not observe other metals also and it is believed that (low due to BMG is obtained for generation in BMG
The viscosity or corresponding flow stress obtained), and therefore, the intimate contact between roller and BMG raw material.Therefore, in order to reduce in heat
Adherency during rolling, it is necessary to reduce adhesion energy.
The invention proposes following strategies to reduce BMG raw material to the adherency tendency of roller:
(1) it reduces microcosmic surface and accumulate-observes that adherency tendency is reduced along with very high surface smoothness.Therefore,
Attempt to reduce adherency tendency, roughness reduces.Firstly, adherency deteriorates, it but is below the roughness compared with mirro finished, is observed
The decline of adherency is arrived；
(2) surface chemistry-is when the roll material of the bad wetting of BMG is used in selection.This means that angle of wetting, the β in equation 7
Greater than 90 degree (equation 7 is always set up).For example, nitride and other ceramic roller surfaces reduce adherency (increasing angle of wetting), and it is golden
Belong to roller surface and promotes adherency.
(3) it is relevant to surface chemistry be BMG raw material oxidation.The oxidized surface of BMG raw material also reduces adherency.For example,
It is found to have the Pt of minimum oxidation tendency57.5Cu14.7Ni5.3P22.5BMG is most strong to roller adherency, and Pd43Ni10Cu27P20BMG adherency
Zr that is significant weaker and being tested44Ti11Cu10Ni10Be25The smallest adherency tendency occurs for BMG alloy, as shown in Figure 15.
(4) another way for preventing BMG from adhering to is can be (in equation (7) by the surface that addition lubricant reduces BMG
γ1-v)。
Figure 15 depicts the Pt of institute's rolling57.5Cu14.7Ni5.3P22.5The photo of sample.As shown in Figure 15,
Pd43Ni10Cu27P20Sample can be adhered to top and bottom roller simultaneously, this causes it to tear along center line.
Method described herein allows to manufacture the ultra-smooth sheet material of the block metal glass with low oxidation ratio.
Once in addition, BMG has been manufactured into big, thin sheet material then other procedure of processings can be carried out so that BMG piece
Material forms more complicated design shape.
For example, Figure 16 depicts the example for manufacturing pattern (in plane or outside plane) in BMG sheet material using patterned rolls.Such as
Shown in Figure 16, preheating steps are passed through in BMG and have processed and passed through this group of heating roller rolling, has then carried out as above retouching in detail
After the stretching step stated, BMG can be processed by one group of subsequent heating roller, which there is setting to exist
In plane thereon or the outer pattern of plane is so that BMG sheet material patterns.When first group of heating roller is by pattern (in plane or plane
When be applied on BMG sheet material outside), this group of patterned rolls are maintained at identical or different processing temperature.
These identical patterns can also be formed by using thermoplastic extrusion as shown in Figure 17 or blow molding method
To manufacture.In a similar way, preheating steps have been passed through in BMG and have processed and passed through this group of heating roller rolling, then carried out
After stretching step, BMG can be subjected to extrusion forming or blow molding processing, as generally known in the art.The reality of these technologies
Example description is for example, the U.S. Patent Publication No. of the U.S. Patent number 8,641,839 of Schroers et al. and Schroers et al.
In 2013/0306262, respective theme passes through reference herein and is incorporated in its entirety.
In addition, forming step can also be carried out so that block metal glass sheet forming is to mold cavity.If it is expected that can carry out
Step is sheared so that block metal glass sheet material is cut into the profile determined by mold cavity.In another preferred embodiment,
Deforming step can be carried out so that the corrugation of block metal glass sheet material is at the deformity out of plane determined by mold cavity.
By using these methods and other patterning methods for being similarly used for BMG or even extremely complex shape
Such as spectacle frame as shown in Figure 18, method described herein manufacture can be used.
In another preferred embodiment of the invention, block metal glass raw material may include the more of the engagement in step b)
A block metal glass block.As shown in Figure 19, the multiple block metal glass blocks for forming " sandwich " can be connect by rolling
It closes.The engagement step can be completely, and plurality of block metal glass block is fully engaged without any gap.It is substituting
Property embodiment in, controllable bonding station is to prevent several pieces of block metal glass in certain engagement positions so that only part
Block metal glass block is engagement.In the method, in one embodiment, multiple material such as salt and polymer can dissipate
Cloth prevents block metal glass block in certain engagement positions in block metal glass block.It can prevent material from connecing in some regions
It closes so that only block metal glass block in part is that the other methods of engagement can also be used in practice of the invention.
The present invention is also generally related to the system for forming block metal glass sheet material by block metal glass raw material, the system
Include:
A) one group of pre-add hot plate, wherein this group of pre-add hot plate can press from both sides block metal glass raw material in-between with pre-add
Hot block metal glass raw material is to being enough to soften block metal glass raw material but does not provide disappearing for block metal glass significantly
The temperature of the crystallization time of consumption；
B) it is maintained at one group of rotary heating roller of the processing temperature of block metal glass, wherein when this group of heating roller rotates
When, heating roller thermoplasticity rolling slave pre-add hot plate therebetween the step of received block metal glass raw material so that block
Glassy metal raw material is thinning at block metal glass sheet material；With
C) drawing mechanism can pull down in controlled velocity and extend away from the block metal glass through rolling of this group of heating roller
Sheet material.
As described above, drawing mechanism is mobile relative to negative temperature gradient, wherein when block metal glass is from this group of heating roller
When drawing or stretching, it is cooled to the temperature of the processing temperature lower than BMG.
In one embodiment, drawing mechanism includes the draw-off mechanism of speed control, wherein when block metal glass piece
When material leaves from this group of heating roller, the draw-off mechanism of speed control pulls block metal glass sheet material.The drawing mechanism preferably with
This group of heating roller faster rate drawing block metal glass sheet material is advanced through than block metal glass.
In another embodiment, drawing mechanism includes one group of rotatable chill roll.In this embodiment, which can
Rotation chill roll is maintained at the lower temperature of than this group heating roller and when block metal glass sheet material leaves this group of heating roller
Receive block metal glass sheet material therebetween.This group of chill roll is further preferably with the faster rate rotation of than this group heating roller.
Similarly, as described above, after rolling and stretching step, system of the invention may additionally include block metal glass piece
Pattern is applied to one group of rotatable patterned rolls on block metal glass sheet material after leaving drawing mechanism by material.In alternatives
In, after rolling and stretching step, various processing and formings can be carried out so that pattern to be applied on block metal glass sheet material.
In one embodiment, system of the invention may include that the system of multiple series connections is thin continuously to produce
Block metal glass sheet material.For example, at least one set of other heating roller and at least one set that the system may include multiple stations are in addition
Chill roll, wherein block metal glass is further thinning.If desired, one group of preheater plate can be located at least one set of other add
Before hot-rolling.However, if block metal glass sheet material is held in enough temperature of the rolling between this group of heating roller, every
Preheater plate may not be necessary between a station.As described herein, " cold " roller is only in relation to being kept by this group of heating roller
Processing temperature is cold.If block metal glass sheet material is not significantly cooled between next subsequent station, may not be needed
Additional preheater step.Therefore the best configuration of this group of preheater plate in system, this group of heating roller and this group of chill roll can
It is determined by those skilled in the art.
This group of heating roller optionally includes providing the surface covering on smooth, non-stick surface on it.Prevent block golden
Belong to glass adhesion to heating roller other methods discussed above.In addition, this group of heating roller preferably is contained in block metal glass
The sufficiently solid hard metal of processing temperature.
This group of chill roll can have rough surface, so that the group when block metal glass sheet material leaves this group of heating roller
Chill roll keeps a firm hand on block metal glass sheet material.
Figure 12 and 13 depicts the figure of preheater plate and this group of heating roller according to the present invention.As shown in Figures 12 and 13, in advance
Hot device plate 2 and 4 is configured to receive block metal glass raw material.As described above, gravity, which can be used only, in preheater plate clamps block
Glassy metal raw material or optionally using the tool of additional offer pressure to provide preheater plate and block metal glass
More intimate contact between raw material.
Servo motor 6 controls the rotation of this group of heating roller 8 and 10.Load and displacement sensor 12 can be used for providing to roller
Position feedback.One group of jack screw can be used for controlling the group based on from load and the received information of displacement sensor 12
Gap between heating roller 8 and 10.
Figure 13 depicts the exploded view of the key component of roller 8 and 10.As shown in Figure 13, cartridge heater 16 together with
Thermocouple 18 is placed longitudinally along roller 8 and 10 together.Preheater plate 2 and 4 respectively also has cartridge heater 20 and passes through them
Thermocouple.
Figure 14 depicts the example of pre-add hot plate 2 and 4 according to the present invention.Measuring scale is in inches.
As described herein, the present invention allows to manufacture big, the thin block metal glass sheet material with uniform thickness.This
Outside, the present invention allows to manufacture the block metal glass item with uniform thickness.The present invention also allows in block metal glass sheet material
In further manufacture complicated pattern.In addition, the present invention allows continuously to manufacture arbitrarily complicated shape.Finally, the present invention also permits
Perhaps same type or different types of block metal glass is engaged by hot rolling.Manufacture has desired feature, texture, thickness
Other purposes of the invention of degree and the block metal glass sheet material of configuration are known to the skilled person and are in
In the scope of the present invention.
It should be understood that following following claims be intended to cover all upper and specific features of the invention described herein and
All statements (on language) of the scope of the invention can be fallen in-between.
Claims (29)
1. the method for manufacturing block metal glass sheet material, the described method comprises the following steps:
A) block metal glass raw material is preheated to and is enough to soften block metal glass raw material but bulk metal is not provided
The temperature of the consumption crystallization time of glass, wherein 0.8 times glass transition temperature of the pre-heating temperature in block metal glass raw material
Spend TgBetween 1.4 times of glass transition temperature, the glass transition temperature is with a degree Celsius measurement；With
B) the thermoplasticity ground roll between one group of heating roller of the processing temperature in the supercooling liquid phase region for being maintained at block metal glass
Roll preheated block metal glass raw material；And
C) this group of heating roller post-tensioning block metal glass sheet material is left in block metal glass sheet material；
Reduce the thickness of block metal glass raw material wherein to generate block metal glass sheet material；With
Wherein processing conditions is such in step a) to c) period, so that keeping reynolds number Re < 10 of block metal glass-3。
2. occurring according to the method described in claim 1, being wherein stretching in negative temperature gradient.
3. occurring at a controlled rate according to the method described in claim 1, wherein stretching.
4. according to the method described in claim 1, wherein repeating the expectation that step a) obtains block metal glass sheet material to c)
Thickness.
5. according to the method described in claim 1, wherein step a) and b) carrying out in air.
6. according to the method described in claim 1, wherein thermoplasticity rolling step reduce thickness disturbance, can be in subsequent drawing
It stretches in step process and is increased with magnitude.
7. according to the method described in claim 1, wherein block metal glass raw material includes multiple block metal glass blocks.
8. according to the method described in claim 7, wherein the multiple block metal glass block engagement in step b).
9. according to the method described in claim 7, wherein only the part block metal glass block is engagement.
10. extending according to the method described in claim 1, wherein stretching the bending for increasing block metal glass sheet material with rolling
Property.
11. according to the method described in claim 1, further comprising that pattern is applied to block metal glass piece after step c)
The step of material.
12. according to the method for claim 11, wherein by one group of patterned rolls rolling block metal glass sheet material with incite somebody to action
Pattern is applied on block metal glass sheet material, and wherein this group of patterned rolls are maintained at the supercooled liquid phase of block metal glass sheet material
Processing temperature in area, wherein pattern is applied on block metal glass sheet material by this group of patterned rolls.
13. carrying out forming step according to the method for claim 11, wherein after step c) pattern is applied to block
On glassy metal sheet material.
14. carrying out forming step so that block metal glass piece according to the method for claim 11, wherein after step c)
Material is formed into mold cavity.
15. according to the method for claim 14, wherein carry out shearing step with by block metal glass sheet material be cut by
The profile that mold cavity determines.
16. according to the method for claim 14, wherein carry out deforming step so that block metal glass sheet material corrugation at by
The deformity out of plane that mold cavity determines.
17. according to the method for claim 11, wherein pattern has the length dimension less than 1mm.
18. according to the method for claim 17, wherein pattern has the length dimension less than 0.5mm.
19. according to the method for claim 11, wherein pattern includes mold cavity.
20. the system for manufacturing block metal glass sheet material, the system comprises:
A) one group of pre-add hot plate, wherein this group of pre-add hot plate can clamp block metal glass raw material therebetween with pre-add heat block
Body glassy metal raw material is to when being enough to soften block metal glass raw material but do not provide the consumption crystallization of block metal glass
Between temperature, wherein 0.8 times glass transition temperature T of the pre-heating temperature in block metal glass raw materialgWith 1.4 times of glass
Change between transition temperature, the glass transition temperature is with a degree Celsius measurement；
B) it is able to maintain one group of rotary heating roller of the processing temperature in the supercooling liquid phase region of block metal glass, wherein when
When the rotation of this group of heating roller, the heating roller thermoplasticity rolling slave pre-add hot plate therebetween the step of received bulk metal glass
Glass raw material is so that block metal glass raw material is thinning at block metal glass sheet material, and wherein this group of heating roller includes hard metal；With
C) drawing mechanism can stretch the block metal glass sheet material through rolling for leaving this group of heating roller.
21. system according to claim 20, wherein drawing mechanism is moved along negative temperature gradient.
22. system according to claim 20, wherein the drawing mechanism can be pulled down in controlled velocity extends away from the group
The block metal glass sheet material through rolling of heating roller.
23. system according to claim 22, wherein drawing mechanism is to be advanced through the group than block metal glass sheet material
The faster rate of heating roller pulls block metal glass sheet material.
24. system according to claim 22, wherein drawing mechanism includes one group of rotatable chill roll, and wherein the group can revolve
Turn chill roll be maintained at the lower temperature of than this group heating roller and when block metal glass sheet material leaves from this group of heating roller
Block metal glass sheet material is received between it.
25. system according to claim 22, wherein drawing mechanism includes clamping device, when block metal glass sheet material from
When this group of heating roller leaves, the clamping device receives block metal glass sheet material in-between.
26. system according to claim 24, wherein the rotatable chill roll of the group is with than this group faster rate of heating roller
Rotation.
27. system according to claim 20 further comprises one group of rotatable patterned rolls, wherein in bulk metal glass
After glass sheet material leaves drawing mechanism, pattern is applied on block metal glass sheet material by the rotatable patterned rolls.
28. system according to claim 27, wherein one group of rotatable patterned rolls are maintained at block metal glass
Supercooling liquid phase region in processing temperature.
29. system according to claim 20, wherein preheating, rolling and stretching carry out in air.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361919158P | 2013-12-20 | 2013-12-20 | |
| US61/919,158 | 2013-12-20 | ||
| US201462025558P | 2014-07-17 | 2014-07-17 | |
| US62/025,558 | 2014-07-17 | ||
| PCT/US2014/071408 WO2015134089A2 (en) | 2013-12-20 | 2014-12-19 | A method and system for fabricating bulk metallic glass sheets |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106488809A CN106488809A (en) | 2017-03-08 |
| CN106488809B true CN106488809B (en) | 2019-06-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480073984.4A Active CN106488809B (en) | 2013-12-20 | 2014-12-19 | Manufacture the method and system of block metal glass sheet material |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20160346819A1 (en) |
| EP (1) | EP3083090A4 (en) |
| KR (1) | KR20160086946A (en) |
| CN (1) | CN106488809B (en) |
| WO (1) | WO2015134089A2 (en) |
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|---|---|---|---|---|
| JP6328097B2 (en) * | 2012-03-23 | 2018-05-23 | アップル インコーポレイテッド | Amorphous alloy roll forming of raw materials or component parts |
| US20170087610A1 (en) * | 2015-09-30 | 2017-03-30 | Apple Inc. | Thermoplastic forming of cold rolled alloys |
| EP3708270A1 (en) * | 2019-03-12 | 2020-09-16 | Heraeus Deutschland GmbH & Co KG | Mouldings with uniform mechanical properties comprising a metallic solid glass |
| CN111468729B (en) * | 2020-04-06 | 2021-12-31 | 华中科技大学 | Powder rolling method and device for amorphous alloy |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4782994A (en) * | 1987-07-24 | 1988-11-08 | Electric Power Research Institute, Inc. | Method and apparatus for continuous in-line annealing of amorphous strip |
| US5207962A (en) * | 1991-06-25 | 1993-05-04 | Applied Extrusion Technologies, Inc. | Method of making apertured film fabrics |
| US20060102315A1 (en) * | 2002-09-27 | 2006-05-18 | Lee Jung G | Method and apparatus for producing amorphous alloy sheet, and amorphous alloy sheet produced using the same |
| CN1327990C (en) * | 2002-09-27 | 2007-07-25 | 学校法人浦项工科大学校 | Method and apparatus for producing amorphous alloy sheet, and amorphous alloy sheet produced using the same |
| CN101257982A (en) * | 2005-09-08 | 2008-09-03 | 艾尔坎技术及管理有限公司 | Forming tools |
| EP1933995B1 (en) * | 2005-09-08 | 2012-01-25 | Constellium Switzerland AG | Forming tool |
| WO2008100583A1 (en) * | 2007-02-13 | 2008-08-21 | Yale University | Method for imprinting and erasing amorphous metal alloys |
| US8298647B2 (en) * | 2007-08-20 | 2012-10-30 | California Institute Of Technology | Multilayered cellular metallic glass structures and methods of preparing the same |
| CN101420826B (en) * | 2007-10-25 | 2012-10-10 | 鸿富锦精密工业（深圳）有限公司 | Case and surface treating method |
| US8613813B2 (en) * | 2008-03-21 | 2013-12-24 | California Institute Of Technology | Forming of metallic glass by rapid capacitor discharge |
| AU2011237361B2 (en) * | 2010-04-08 | 2015-01-22 | California Institute Of Technology | Electromagnetic forming of metallic glasses using a capacitive discharge and magnetic field |
| CN201669392U (en) * | 2010-05-18 | 2010-12-15 | 南昌市南方连铸工程有限责任公司 | Semi-solid casting-rolling double-roll type thin strip bloom conticaster |
| CN103328675B (en) * | 2010-12-23 | 2016-01-06 | 加利福尼亚技术学院 | Formed by the sheet material of the metallic glass of rapid capacitor discharge |
| US20130025746A1 (en) * | 2011-04-20 | 2013-01-31 | Apple Inc. | Twin roll sheet casting of bulk metallic glasses and composites in an inert environment |
| US20140345754A1 (en) * | 2011-09-16 | 2014-11-27 | Crucible Intellectual Property Llc | Molding and separating of bulk-solidifying amorphous alloys and composite containing amorphous alloy |
| US10047420B2 (en) * | 2012-03-16 | 2018-08-14 | Yale University | Multi step processing method for the fabrication of complex articles made of metallic glasses |
| JP5964639B2 (en) * | 2012-04-13 | 2016-08-03 | 株式会社中山アモルファス | Amorphous alloy plastic working method and plastic working apparatus |
| US9375788B2 (en) * | 2012-05-16 | 2016-06-28 | Apple Inc. | Amorphous alloy component or feedstock and methods of making the same |
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- 2014-12-19 CN CN201480073984.4A patent/CN106488809B/en active Active
- 2014-12-19 EP EP14884848.4A patent/EP3083090A4/en not_active Withdrawn
- 2014-12-19 KR KR1020167016497A patent/KR20160086946A/en active Search and Examination
- 2014-12-19 WO PCT/US2014/071408 patent/WO2015134089A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| EP3083090A4 (en) | 2017-06-07 |
| CN106488809A (en) | 2017-03-08 |
| EP3083090A2 (en) | 2016-10-26 |
| KR20160086946A (en) | 2016-07-20 |
| WO2015134089A2 (en) | 2015-09-11 |
| WO2015134089A3 (en) | 2015-12-03 |
| US20160346819A1 (en) | 2016-12-01 |
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