CN106488809A

CN106488809A - The method and system of manufacture block metal glass sheet material

Info

Publication number: CN106488809A
Application number: CN201480073984.4A
Authority: CN
Inventors: J·施勒尔斯; 刘泽; M·卡尼克; 陈文�; P·波尔迪尼提卡瑟姆; R·M·O·莫塔; J·凯特卡尤; 李宁
Original assignee: Yale University
Current assignee: Yale University
Priority date: 2013-12-20
Filing date: 2014-12-19
Publication date: 2017-03-08
Anticipated expiration: 2034-12-19
Also published as: EP3083090A4; WO2015134089A2; KR20160086946A; WO2015134089A3; EP3083090A2; CN106488809B; US20160346819A1

Abstract

The present disclosure describe how making glassy metal deformation to manufacture method and the hardware of thin and large-area metal glass sheet in low power and under the conditions of stabilizing.Which is based on thermoplasticity rolling and the combination of stretching, and is normally combined with pre-add thermal means.The Main Patterns of deformation depend on BMG condition such as thickness, viscosity and crystallization time.

Description

The method and system of manufacture block metal glass sheet material

Cross-Reference to Related Applications

This application claims the U.S. Provisional Application No. 61/919 of No. 20 submissions of in December, 2013,158, and July 17 in 2014 The rights and interests of number U.S. Provisional Application No. 62/025,558 that submits to, the theme here of each of which is by quoting with which in full simultaneously Enter.

Invention field

The present invention relates generally to make glassy metal deform to manufacture the method for glassy metal sheet material, web and band and set Standby.

The statement that studies with regard to federal funding or develop

The present invention is according to the W911NF-11-I-0380 authorized at AUS research, is made using governmental support. U.S. government has some rights in the present invention.

Background of invention

Block metal glass (BMG), its are also referred to as bulk-solidifying amorphous composition, are class amorphous metals Alloy material, its are considered as the material likely for broad spectrum application, this be the property excellent due to them 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, its are 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 conveniently by using standard Calorimetric Techniques (such as DSC (differential scanning calorimetry) Measurement, is determined with 20 DEG C/min.

Generally, larger Δ Tsc is related to relatively low critical cooling rate, although the scattering of significant quantity (scatter) exists Δ Tsc value more than 40 DEG C is present.Have more than 40 DEG C of Δ Tsc, and preferably greater than 60 DEG C, and still more preferably 70 DEG C or more The bulk-solidifying amorphous of high Δ Tsc are very desired, and this is formed due to being relatively easy to.In supercooling liquid phase region, Bulk-solidification alloy acts like high-viscosity fluid.The viscosity of the bulk-solidification alloy with wide supercooling liquid phase region from 10¹²Pa s (in glass transition temperature) drops to 10⁷Pa s and drop to 10 in some cases⁵Pa·s.Heating block Solidified superalloy to cause to crystallize more than crystallization temperature and the loss immediately of alloy excellent properties and its can not re-form.

The superplasticforming (SPF) of amorphous metal alloy includes to be heated to SCLR and make under an applied pressure Its shaping.The method similar to the processing of thermoplastic, the formability being wherein inversely proportional to viscosity with temperature increase and Increase.However, with thermoplastic conversely, high viscosity amorphous metal alloy is metastable and finally crystallizes.

Due to some reasons, it is necessary to avoid the crystallization of amorphous metal alloy.First, amorphous metal alloy is which reduced Mechanical performance.From from the perspective of processing, crystallization limits process time of thermoforming operations, this be due in crystalline material In flowing higher than the order of magnitude of flowing in liquid amorphous metal alloy.The crystallization of various amorphous metal alloys is moved Mechanics causes process time in the range of viscosities between minute and hour.This causes super plastic forming method to become can be The method for fine-tuning that convenient time specification is carried out so that the net shaping of complex geometry is possibly realized.

Form amorphous metal alloy ability with treating thermoplasticity is described by its formability, and formability is directly related to In temperature dependent viscosity and the parameter of the interphase interaction of crystallization time.During the TPF of amorphous metal alloy, it is necessary to Crystallization is avoided, because which causes amorphous metal alloy property-deterioration and slows down its formability.Therefore, close 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 being processed further) is one of most important shape of metal. Especially, for glassy metal, sheet is high expectations, because they are thin in a dimension, and such In geometry, block metal glass (BMG) often shows bend ductility.For example, have shown that thickness be～1mm in Bend ductility is shown etc. the BMG of scope.

However, BMG sheet material, especially the manufacture of big BMG sheet material is always challenging, and prior art is not also opened up Illustrate that size exceedes the sheet material of about 10cmx10cm.

Conventional casting is not particularly suited for the manufacture of the BMG sheet material manufactured by rolling method, because the method needs lance The requirement of shield-quickly cooled down to avoid crystallization and Slow cooling on the other hand to fill whole mold cavity on the one hand.Double Roller casting must be carried out in high vacuum or protective atmosphere, and challenging control problem.The cold rolling of BMG be very Limited because at room temperature BMG by formed shear band plastically high localized deform, wherein the overwhelming majority answers changed situation Portion, different from the uniform deformation needed for rolling.Therefore, during cold rolling realize deformation be highly non-uniform, And thickness is exceeded to the raw material of about 1mm, cause directly rupture.

(T at the temperature in the supercooling liquid phase region of specific BMG_g<T<T_x) deformation be also explored for shaping and adding Work.At the temperature in supercooling liquid phase region, for actual strain speed, BMG is in low stress ,～1/100 room-temperature yield strength Lower homogeneous deformation, and utilizing for so low flow stress be explored for manufacturing thin BMG disk.

Trial is made with rolling BMG in supercooling liquid phase region.Most successful is wherein to be heated by heating plate Method, the heating plate together with raw material pass through roller.However, forever connecing with the heating plate for clamping and thereby heating BMG in this BMG Touch.Therefore, the principal benefits (reduction of contact area of the mould (roller) and material between) of rolling are sacrificed, and to deform be phase When limited.The maximum and most thin block (piece) obtained by the method is about 7cmx5cm, and thickness is for about 0.4mm.Due to Raw material is permanent contact with mould (heating plate), can not possibly also realize big thin sheet material with the technology.

Thermoplastic molding is processed, wherein BMG and mould permanent contact, for constant pressure, the increase of radius and when Between ^^1/8Proportional.Or unpractiaca long-time (exceeding well over crystallization time, which defines maximum process time) is with reality therefore, Existing large radius is pressure necessary or that needs are impractically high.Therefore, wherein whole BMG is uncomfortable with the technology of contacting dies Share in the big and thin BMG sheet material of manufacture.

The U.S. Patent number 8 of Prest et al., 485,245, its theme here is incorporated by with which by quoting, and is described Melting BMG alloy is poured onto the motlten metal with the density higher than BMG melt and lower temperature in float chamber To disperse and solidify BMG melt the method for forming BMG sheet material in bath.The technique depends on the solidification of BMG melt.

However, it is difficult to control thickness, it is the gravity by BMG melt and molten bath due to the balance sheet thickness of gained that this is Limit with surface tension.Additionally, inert gas environment and/or vacuum are needs in molten alloy room and float chamber.

The U.S. Patent Publication No. 2013/0025746 of Hofmann et al., its theme here is by quoting with which in full simultaneously Enter, the method for describing to manufacture BMG sheet material by the twin roller casting of BMG melt in inert environments.The method includes to melt BMG melt injection enter chilling roller in so that metal glass melt is frozen into sheet material.As extra selection, the BMG piece for leaving Material can form thinner sheet material by one group of follow-up roller thermoplasticity ground further.

In the process, such as get off to process BMG melt：First by chilling roller for solidified cast, and after then passing through One group of continuous hot-rolling is for hot rolling.The twin roller casting method make BMG melt be frozen into sheet material and must in a vacuum or Complete in inert environments.Additionally, be not desired by the thickness of the BMG sheet material of twin roller casting, because which is often non-equal Even, with less than about 200 μm of typical thickness.After twin roller casting, also needed by one group of follow-up roller thermoplasticity rolling Rolling stress that will be very high is deform fine sheet and obtain thinner sheet material further.

The U.S. Patent Publication No. 2014/0064043 of Tsuchiya et al., its theme here is by quoting with which in full simultaneously Enter, the method for describing to manufacture clock spring, which passes through for BMG melt list roller to be cast as sheet material, then superplasticity rolling BMG piece Material is to eliminate the aperture on the BMG clock spring surface that casting causes.

Similar to Hofmann, technique carries out to hot-rolling and depends on solidification of the BMG melt in inert environments from chilling roller. This cause when BMG wherein air be maintained on the surface of BMG or internally in the state of solidify when BMG sheet surface on little Hole.Thickness is also uncontrollable (that is, be heterogeneous and usually less than about 200 μm).The hot rolling step of superplasticity is only designed Be for making the smooth surface of BMG sheet material；Which deforms can not sheet material, due to high hydrostatic stress shape during hot rolling State.Finally, the stretching of single shaft thermoplasticity is not applied.

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, its respective theme here is incorporated by with which by quoting, and describes use quick in several milliseconds The method that capacitor discharge technology is quickly heated and forges block metal glass.Although the method quickly can soften BMG, But the pyroplastic deformation or forging stress for the method be very high, this be due to the Large strain in short time scale Speed and the high hydrostatic stress under casting, therefore limiting which is used for manufacturing big BMG sheet material.

Therefore, exist in this area under actual condition (for example, in atmosphere and under practicable pressure) with Controlled mode can make glassy metal deformation to produce the method for the block metal glass sheet material with any thickness and size Demand.Additionally, there is the demand of the manufacture method that can produce big, thin block metal glass sheet material in this area.

Summary of the invention

The object of the invention is to produce block metal glass sheet material.

It is another object of the present invention to block metal glass sheet material of the manufacture with uniform thickness.

It is another object of the present invention to manufacturing agglomerate body glassy metal sheet material under favourable processing conditions.

The present invention still another object is that block metal glass sheet material of the manufacture with complex pattern.

The present invention still another object is that manufacture block metal glass web.

The present invention is still another object is that by hot rolling engagement block glassy metal sheet material or web.

The system that still another object is that for manufacturing block metal glass sheet material and web of the present invention.

For this purpose it is proposed, in one embodiment, the present invention relates generally to the method for manufacturing block metal glass sheet material, should Method is comprised the following steps:

A) block metal glass raw material being preheated to be enough to soften block metal glass raw material, but block is significantly provided The temperature of the crystallization time of the consumption of body glassy metal；With

B) thermoplasticity ground rolling is being maintained between the one of processing temperature of block metal glass group of heating roller through preheating Block metal glass raw material；

Wherein reduce the thickness of block metal glass raw material to produce block metal glass sheet material.

The present invention is also generally related to the system for manufacturing block metal glass sheet material, and the system includes:

A) one group of pre-add hot plate, wherein the group pre-add hot plate can clamp block metal glass raw material therebetween to preheat But block metal glass raw material does not provide to be enough to soften block metal glass raw material significantly the consumption of block metal glass Crystallization time temperature；

B) one group of rotary heating roller of the processing temperature of block metal glass is maintained at, wherein when the group heating roller rotation When, heating roller thermoplasticity ground rolling from pre-add hot plate the step of receive block metal glass raw material therebetween so that block is golden Category frit thinning become block metal glass sheet material；With

C) drawing mechanism, its can be in the drop-down block metal glass through rolling for extending away from the group heating roller of controlled velocity Sheet material.

Brief description

For a more complete understanding of the present invention, the following explanation related to accompanying drawing is referred to, wherein:

Figure 1A, 1B, 1C and 1D are depicted makes glassy metal in the thinning multiple methods of their subcooled liquid state.

Fig. 2 depicts the two methods of BMG process technology.

Fig. 3 A and 3B illustrate the relation between formability and processing temperature.

Fig. 4 A and 4B depict the maximum change preheated to being realized during hot rolling with insignificant tensile force The effect of shape.

Fig. 5 depicts temperature curve of one step (routine) processing scheme together with the processing scheme of the present 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 the schematic diagram combined by rolling system with drawing process.

Fig. 9 depicts the contrast of the rolling force for identical speed (3mm/s) and tensile force.

Figure 10 depicts the maximum shear stress of the function under thermoplasticity rolling as sheet thickness and maximum hydrostatic pressing The contrast of power.

Figure 11 A depicts the Zr of institute's rolling₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅BMG sheet material and Figure 11 are depicted and are being removed surface oxidation Zr afterwards₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅BMG sheet material.

Figure 12 depicts the rolling installation for BMG material according to the present invention.

Figure 13 depicts the exploded view of the key component of the rolling device according to the present invention.

Figure 14 depicts the example of the pre-add hot plate according to the present invention.

Figure 15 depicts the Pd of institute's rolling₄₃Ni₁₀Cu₂₇P₂₀Sample.

Figure 16 depicts the example using patterned rolls (in plane or outside plane) manufacture pattern in BMG sheet material.

Figure 17 is depicted and is molded using thermoplastic extrusion or blow molding method manufactures the example of pattern in BMG sheet material.

Figure 18 depicts the example of the spectacle frame patterned in the BMG sheet material that processes 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, although not every element can be made marks in each figure, but all with identical reference numerals Element represents similar or identical part.

The specific descriptions of preferred embodiment

The present invention relates generally to make glassy metal deform to manufacture large area bulk metal in low power and under the conditions of stabilizing Glass sheet and the method and apparatus of block metal glass bar and band." sheet material " refers to wide extension or block metal glass Surface." web " or " band " refers to grow narrow one piece block metal glass.In both cases, block metal glass piece Material or web are through manufacture to have the less than about thickness of 1mm.

As described previously for the prior art based on thermoplasticity rolling, roller is typically cold (～room temperature), and this is than desired Rolling temperature is much lower.Therefore, after rolling, BMG is cooled down and its flow stress quickly increases.The critical aspects of the present invention are Establishment opposite-when roller is close to, BMG material temperature increases and considers that the consumption of the formability before contact roller is optimized Its increased amount.This minimizes and reaches the time needed for rolling temperature and optimize the viscosity during rolling to allow greatly Deformation, its cause separate and laminar flow be achieved.

Surprisingly it has been found that the BMG sheet material for obtaining great Bao by using only hot rolling is difficult, this be by In the hydrostatic pressure needed for actual shearing deformation is reached, (wherein η is viscosity, and U is rolling speed, and R and h is roller and sheet thickness Radius).Hydrostatic pressure can be considered as loss, and this is to be only dependent upon the gradient of pressure due to detrusion；Most of folder Only hydrostatic extrudes BMG without any permanent deformation to clamp force.Common size and thickness are reduced, hydrostatic pressure is consumed The power that applied of the overwhelming majority and more than the producible pressure of clamping force by actual obtainable hot rolling mill.Letter speech It, thermoplasticity rolling does not allow for manufacturing the BMG sheet material that oversize is that 20cmx20cm and thickness are less than about 0.05cm in itself, 10 are less than even for those actual obtainable viscosity of considerably less minimum⁷The glassy metal of Pa s is also such.

The stretcher strain that present inventors have found that BMG is that deformation force (wherein essentially all of is applied Power be used for deform) effective result for using.However, when only using stretching, observing unstability (constriction), especially Under high draw speed.Therefore, thickness change is unacceptably high and is deteriorated because of multi-pass processing as shown in Figure 1A.

However, when along the one or more hot rolling of negative temperature gradient combination and drawing under controlled speed (not being power) When stretching, so that the power of block metal glass deformation is strongly reduced, and big, thin sheet material can be obtained.Additionally, the combination cause high Stability, and the very little thickness change of the sheet material through manufacturing.

Known quick cooling can affect the mechanical performance of BMG.But the deformation that did not also report in process of setting also may be used Impact mechanical performance.The inventors found that and method described herein is used, sample deformations are solidified until which.Additionally, right The bend ductility higher than unstretched sample is measured in the sample of drawn in process of setting.

The present invention relates generally to the method and system of the glassy metal sheet material for manufacture with controlled dimensions.Glassy metal Deform in the low power for manufacturing thin and large-area metal glass sheet and under the conditions of stabilizing.Greatly (for example, the present invention had both had production At least 20cmx40cm, depending on specific BMG) but thin (that is, thickness is less than about 1mm, preferably less than about 0.5mm, most preferably little In about 0.1mm and even more thin, depending on specific BMG) glassy metal sheet material ability.

The present invention be based on thermoplasticity rolling technology, its optionally, it is preferred that combining with stretcher strain.Which is based on one Plant or multiple thermoplasticity rollings and stretching combining (with Combination of Methods is preheated).The Main Patterns of deformation depend on BMG bar Part such as thickness, viscosity and crystallization time.Method described herein avoid sheet material (particularly further described below by The big and thin sheet material that BMG with low formation makes) crystallize in manufacture process.By preheating, reduce and consumed Available process time, this are allowed using thick raw material.During hot rolling, deformation is used for reduce thickness to less than us The only very limited amount of deformation for relying on；Minimum requirements is the mitigation disturbance in terms of thickness.

Therefore, in one embodiment, the present invention relates generally to the method for manufacturing block metal glass sheet material, the method Comprise the following steps:

In the first procedure of processing, glassy metal is heated to 0.8T_g<T_Preheat<1.4T_g(T_g:Heated with 20K/min Glass transition temperature in journey, by DEG C in terms of) temperature with pre-add hot charge BMG for subsequent rolling step.The pre-add Heat step reduces the heat time needed for rolling and has softened BMG, and this causes effectively heat transfer between roller and BMG raw material, and Thus 0.7T is quickly heated up to_X<T_Processing<1.3T_X(T_x:With the crystallization temperature in 20K/min heating process, by DEG C in terms of) roller temperature Degree.If sheet material has been thin, such as after several passages, when thickness is less than 1mm, the preheating steps become less Effectively (or even can be skipped).Subsequently, BMG raw material is in 0.7T_X<T_Processing<1.3T_XThe hot rolling of temperature.

Hot rolling is used for making raw material thinning, but works asBecome not have very much when (mainly for fine sheet) Effect, wherein R is the radius of roller, and Δ h and h is that thickness reduces and thickness respectively, as hydrostatic pressure increases ground in lubrication near field Very fast.Generally, rolling force is less than 10% to the contribution being plastically deformed in that region.However, another benefit of hot rolling Be can reduce any cause " necking down " instable disturbance (original depth change), this contributes to stabilizing subsequent stretching Process.

After block metal glass sheet material is left from the group heating roller, block metal glass sheet material optionally it is preferred that It is exposed to tensile force.Surprisingly, the tensile force generally than glassy metal hot rolling to realize needed for identical deformation rate Clamping force much smaller.Tensile force is applied whole thermograde and block metal glass sheet material is moved along thermograde. This stabilizes processing and prevents instable generation during correlation is thinning.

Stabilize stretching one require be stretching in speeds control under conditions of occur, rather than power control condition Lower generation.Therefore, all of tensile force is used for stretcher strain, and in order to realize similar deformation rate during hot rolling, Very big hydrostatic pressure must be applied.The power applied by establishing hydrostatic pressure does not make raw material thinning and can be considered to damage Lose.Therefore, significantly less than the clamping force applied in hot rolling process, particularly BMG raw material is thin to tensile force wherein Later phases.

Therefore, the BMG sheet material of Bao He great can be realized by the rolling of merging as herein described and drawing process.Therefore, deform The more effective BMG alloy using with much broader scope of power (that is, even has up to 10¹⁰Pa s is (actual achievable ) minimal viscosity those) sheet material can be formed, this is by being impossible based on thermoplastic rolling.

Surprisingly it has been found that deformation passes through by the free body for improving bulk modulus to the ratio generation of modulus of shearing Product or equivalent amount also affect the mechanical performance of BMG.If it is only more prolonging for hot rolling that the solidification in drawing process causes than BMG The BMG of malleability.Therefore, method described herein can produce the BMG with increased ductility, even if in common processing conditions During, they can also be fragility.For example, it was discovered that stretching rolling can be by 0.8mm Zr₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅Bulk metal The bend ductility of the band of glassy alloy increaseds to over 3% from less than 2%.

Such method is realized minimizing formability consumption before raw material contact roller, and is stabilizing and be used for by heat Distortional stress needed for the stretching of Negotiation speed control makes in the thermograde of the thicker raw material of rotary rolling mill step auxiliary is minimum Change.

Figure 1A, 1B, 1C and 1D are depicted makes glassy metal thinning and wherein stretch in their subcooled liquid state Multiple methods that Negotiation speed control (rather than power control) is realized.Figure 1A (situation 1) illustrates the constant drawing in uniform temperature Stretch, cause overall necking down and the non-uniform thickness of raw material.Figure 1B (situation 2) illustrates the temperature gradient field only using stretching.Such as Shown in Figure 1B, do not having along in the drawing process of the hot rolling of thermograde, the typical presence of the surface defect on BMG raw material Serve as " disturbance ".These disturbance sustainable growths in drawing process, cause localized necking behavior.Fig. 1 C (situation 3) is illustrated By very limited amount of strain not along the hot rolling of thermograde stretching, can be produced so that the deformation of BMG raw material, this is because Very high hydrostatic pressure in hot rolling.Finally, Fig. 1 D (situation 4) illustrates that disturbance can by merging hot rolling and stretching It is substantially eliminated and can realize much higher strain and the pyroplastic deformation of stable state.

Fig. 2 depicts the two methods of BMG process technology.Path 1 is to rely on the quick quenching of liquid melt with shape Become the liquid cast technique of BMG, and path 2 depends on the thermoplastic forming of BMG in subcooled liquid state.

The prior art of the BMG sheet material that is processed based on liquid condition for manufacture, such as twin roller casting, single roller casting, note Penetrating shaping or melted melt being toppled in balneation, the processing method for all passing through path 1 is carried out.As described above, path 1 exist some Major defect, for example very high temperature (higher than fluid temperature), quick cooling to avoid crystallizing (narrow process window), to height Vacuum or the demand of inert atmosphere, the control being very limited.

Conversely, many advantages are had based on the BMG sheet material of the processing method in path 2 for manufacture, including much lower temperature Degree and bigger process window.Additionally, it can also be feasible to carry out 2 process technology of path in atmosphere.

The ability of thermoplasticity ground processing BMG is in temperature dependency formabilityMiddle quantization.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 actual manufacture for big, high-quality and thin sheet material as herein described Case.Therefore, make in glassy metal deformation process in thermoplasticity, in order that deformation is maximized, high temperature is selected, in such as 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, for sheet material that rolling is big, it is necessary to make efforts to obtain high temperature Degree, while avoid crystallization.It is probably very challenging experimentally to realize the highly shapable state.

In order to solve the problem, present invention uses optimizing the processing scheme of pre- rolling conditions.Formability be low, and BMG raw material fully soften enable to quickly heat up to rolling temperature (that is, the processing temperature in the specific range of temperatures) and And also optionally, but it is preferable to use stretcher strain is used as primary deformable technique.Stretcher strain needs ratio in hot rolling process The much lower power of middle deformation, and therefore can deform and retain formability in lower temperature.

Preheating for BMG raw material is effective first procedure of processing of methods described herein, and which causes by prior art The bigger possibility deformation of the obtainable entirety of technique.Preheat to insignificant stretching rolling force during hot rolling The effect of (horizontal sheets of sizes) attainable maximum distortion is illustrated schematically in Fig. 4 A and 4B.

Fig. 4 A depict during hot rolling not using any pre-warmed in the case of attainable maximum distortion. As shown in Figure 4 A, without in the case of pre-warmed, BMG raw material is only to be slowly heated to desired rolling temperature, and this makes Become the slow deformation of BMG raw material, while consuming formability.

Conversely, as shown in Figure 4 B, when BMG raw material is from T_PreheatIt is preheated to T_RollingWhen, there is the faster deformation of BMG, this Formability is remained, and the BMG sheet material for causing manufacture big, thin is possibly realized.Preheating steps fully soften BMG so that Roller forms the close contact with BMG, 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 Pa s.In typical thermoplasticity processing scheme, raw material is heated to plus Work temperature.The processing consumption about 1 minute, however, only only a part facilitates the consumption of formability, as shown in Figure 5.This is Close to the temperature province for arranging temperature, T_Arrange± 10%.The reason for must take into only a fraction of be because crystallization time with The increase of temperature and rapid decrease, and when close setting temperature, the rate of heat addition declines.The rate of heat addition and material temperature and set The difference for putting temperature is proportional.Conversely, in the present invention, replace to directly heat to preferable rolling temperature, first by BMG raw material Relatively low temperature is substantially preheated to.Longer in this crystallization time, and the notable formability for getting over fraction is therefore consumed, such as scheme Shown in 3A and 3B.

As shown in figure 5, as 2 step process in the present invention, the consumption of formability in heating process drastically can subtract Little.During current, when being close to T_PreheatWhen (with insignificant formability consumption), the rate of heat addition declines, and wherein As different heating mechanisms is (from T_PreheatTo T_Rolling) consume significant formability temperature province increase.

Present invention utilizes the exponential dependence of crystallization time and temperature.Raw material BMG is heated to wherein crystallization time is Very long (that is, in T_g, crystallization time is about one day or longer) and temperature.However, from from the viewpoint of heat, the temperature is close to In processing temperature.Therefore, the temperature of preheated raw material increase by tens degree realizing only necessarily through the group heating roller plus Work temperature can be by by preheated raw material BMG charging by the group heating roller come real with heating quickly and precisely to increase Existing.Subsequently, cooling can be realized by the free convection of processing environment or can be by gas or liquid are forced at the piece for leaving Strengthen on material.Therefore, the use of preheating steps causes only little bulk deformation and can also cause the infringement to roller.Cause This, block metal glass is preheated to such temperature, wherein the temperature with its in the pot life of processing temperature compared with can To keep long period, its, in one embodiment to 5 times of the youthful and the elderly, preferably at least grow 10 times.In other words, by bulk metal But frit is preheated to and be enough to soften block metal glass raw material the consumption of significantly not facilitating block metal glass The temperature of crystallization time.Meanwhile, in terms of heat, the pre-heating temperature is close to rolling temperature, and BMG raw material is abundant Soften so which can easily thermoplastic ground deformation.

Fig. 6 illustrates Zr₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅The TTT diagram of BMG.As shown in fig. 6, crystallization time with The increase of temperature and rapid decrease.

Fig. 7 illustrates the Zr of maximum in different temperatures through rolling₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅BMG sheet material.Initial feed is complete Portion is all 1.7mm thickness, the disk of 14mm diameter.Indicate the number of passage before crystallization.As shown in Figure 7, use Zr₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅BMG, from from the perspective of rolling, it is optimal process temperature to that define 440 DEG C, to produce possibility Highest thickness reduce and possible most thin sample.

Generally, rolling is carried out with some passages, and its scope can be 3-15 passage.At 440 DEG C, Zr₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅B MG shows the process window of 5-6 minute before crystallization.In a step heating process, at 440 DEG C for every time in total 5-6 ～25 seconds are consumed in minute.Actual rolling (raw material is contacted with roller) depends on such as sheet length, roller radius, rolling speed With for common BMG rolling, actual rolling has spent about 10 seconds.Therefore, about 6 minutes are consumed via the rolling of 10 passages Process time, it is meant that BMG sample can have begun to crystallization.Before BMG sample crystallization, therefore maximum is only about 9 passages.If Have selected nonideal low processing temperature, such as 420 DEG C, process time of 8 minutes is obtainable, and therefore in sample crystallization Before can carry out more than 10 passages.However, the deformation that is realized is low, because the viscosity for dramatically increasing at the lower temperature. Other temperature are also depicted in Fig. 7.

In the present invention, so that pre-heating temperature is optimized paramount but be sufficiently low so that notable offer does not disappear The temperature of the crystallization time of consumption.The temperature is close to processing/rolling temperature so that temperature rapidly can be improved to processing temperature.

As follows the reason for rapid heating capability in the procedure of processing:

(1) temperature is already close to processing temperature, generally>T_Rolling- about 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 achieve Quickly heat transfer.

For example, if BMG preheat at 390 DEG C, rolling, and and then in 440 DEG C of rollings, crystallize and occurred after 35 minutes, this More much longer than the crystallization time specification in 440 DEG C of (without preheating steps) 5-6min.Therefore, formability in heating process Consumption is strongly reduced to pre-heating temperature and can be consumed during rolling step.Therefore, process with a step～10 roads Secondary compare, by using method described herein, before crystallization, BMG raw material can be up to～16 passages with rolling.

As described herein, only just find that the power reached needed for desired thickness reduces is notable by thermoplasticity rolling High, for sheet size (that is, wherein out-of-plane size is than the much smaller size in plane).If however, Add stretching step as shown in Figure 8, then due to tensile force, F can subtract the thickness of sheet material further after leaving from first group of roller Little.

Tensile force can be applied by multiple methods, including for example (that is, being maintained at than heating to " cold " roller by (1) second The processing temperature lower temperature of roller), which is to rotate than first group of higher speed of heating roller to produce tensile force；Or (2) are logical Cross the draw-off mechanism of speeds control.Tensile force is applied to bulk metal glass when block metal glass leaves first group of heating roller Other methods of glass can also be well known by persons skilled in the art.For stretching crucially controlled velocity and negative temperature gradient two Person.

Tensile 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 to decline with the thickness of the sheet material through rolling, drive stress be increased up sheet material fracture.Surprisingly however it was It was found that raw thickness change can reduce so that even some thickness disturbances can be stood before the stretching, without BMG with not Stable mode increases.

Make the requirement of the combinative stability of extruding and stretching rolling as follows:

(1) when BMG sheet material leaves first group of heating roller, negative temperature gradient.So as to, with from first group of heating roller away from From increase, viscosity increases, and therefore deformation resistance increases；

(2) stretch through and accurately control displacement to realize.In other words, stretching is speeds control, rather than power control 's.Generally viscosity is at least substantially constant；With

(3) change of the thickness occurred in drawing process can be planarized by subsequent rolling passage.

Fig. 8 illustrates the schematic diagram of the rolling system combined with drawing process, and wherein second group " cold " roller is used for control The stretching of the sheet material through rolling is so which is thinner.

The deformation mechanism of thermoplasticity rolling and stretching is different.For thermoplasticity rolling, thickness reduction comes from shearing Deformation (similar to extruding flowing), and for stretching, thickness reduction comes 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 tensile force can be calculated.

In following calculating, problem is reduced to 2D problem, i.e. assume that the thickness of sheet material is small enough to than it other Many, and be considered as not squeezable Newtonian fluid for BMG, the BMG deformed in supercooling liquid phase region.Reynolds number1 is actually much smaller than, and therefore body force (body force) such as gravity and Inertia can be ignored.

Based on this, the pressure in rolling can be using determining nothing slip boundary condition as shown in equation (1):

Wherein η is viscosity, and U is rolling speed, and x is along rolling direction, h_m、R、h₁It is the gap between roller respectively, the half of roller Footpath and the sheet thickness in outlet.

Rolling force can and then be calculated according to equation (2):

Tensile force is estimated according to equation (3):

Wherein w is sheet width, and Δ U is the speed difference between two ends of sheet material and L₀It is length, occurs wherein Thickness reduction.

In order to compare rolling and tensile force, Δ h/h₀=40% thickness reduces and is used as example and assumes that roller gap is just The half of beginning sheet thickness, w=10cm, η=10⁶Pa s, U=3mm/s, Δ U=U and L₀=lcm, this for actual control is Reasonably, for example, it is desired to make high-temperature cool down so that stabilization.In one embodiment, in deformation period institute The identical deformation of realization, the difference of the deformation force of thermoplasticity rolling and stretching are at least 10 times.

As a result shown in Figure 9, which compares the rolling force of identical speed (3mm/s) and tensile force, and wherein thickness reduces Δ h/h₀=40%, roller gap is the half of initial sheet thickness, sheet material=10cm and viscosity=10⁶Pa·s.Very astonishing Ground, reaches identical speed in drawing process and the power needed for thickness reduction speed is 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 tensile force.

Based on equation (3), it is apparent that all of tensile force is used for plastic deformation, and for thermoplasticity rolling, shears Stress rather than hydrostatic pressure promote plastic deformation.Function as thickness is compared for identical rolling parameter in fig .9 The maximum shear stress and maximum hydrostatic pressure, as shown in Figure 10.As shown in Figure 10, as sheet thickness reduces, maximum quiet Water pressure significantly quickly increases.Additionally, maximum hydrostatic pressure is often much bigger than the maximum shear stress, it means that by thermoplastic Property the rolling thin sheet material of manufacture become more and more ineffective as sheet material is thinning.15.

One of principal benefits of the present invention are which allows to manufacture sheet material in ambiance.Conversely, proposing before great majority The alternative method for manufacturing sheet BMG part, for example cast including method, twin roller casting and alloy melt shaping, need Vacuum or inert gas or reducing environment is wanted, this is unpractiaca in a manufacturing environment.It is apparent that overwhelming majority BMG is in suggestion Temperature and processing conditions in aoxidize.However, surprisingly finding that 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 the institute's rolling with thickness～450 μm Zr₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅BMG sheet material (T_Rolling- 440 DEG C, T_Preheat=420 DEG C, 13 passages).Figure 11 B is illustrated to remove 1-2 micro- Identical BMG sheet material behind rice surface.

But inventor has found that the surface that oxide is limited to BMG sheet material is desirable for laminar flow.Therefore, the present invention It is limited to cause laminar flow and avoids the processing conditions of turbulent flow.The condition of such flowing can be limited by Reynolds number, wherein The Reynolds number significantly less than 1 is needed to form laminar flow.For technique for rolling, Reynolds number can be calculated asWherein ρ, η and h It is density, viscosity and the thickness of raw material respectively, and U is rolling speed.Laminar flow of the present invention require to include following condition:Respectively It is the rolling thickness of 10 μm of -20mm；Viscosity:10³-10¹⁰Pa s, density:3-20g/cm³；Rolling speed:1-200cm/min, Its all generation Re ≈ 10^-13-10^-3<<1.

Can formally be divided into four groups according to the BMG of present invention processing, even if they fall in non-individual body as shown in table 1 (continuum) in.

The species of table 1.BMG

The demand of stretching depends in part on the desired size of the BMG of particular type and finished product BMG sheet material.

BMG with excellent formability is in T_xShow 10⁶The viscosity of Pa s.Their formability is more than or equal to 10^- ⁴Pa^-1.Preheat rolling thickness raw material (>Needs are remained during starting stage 3mm).Frequently, for the BMG class Type, processing temperature can be selected as relatively low and therefore larger process time to be obtainable and crystallizes and more easily can keep away Exempt from.Stretching is needs only for big sheet material (that is, being multiplied by the size of about 20cm with greater than about 40cm).

BMG with high formability is in T_xShow 10⁶～10⁷The viscosity of Pa s or less.Their formability is for about 10^-4～10^-5.Preheat rolling thickness raw material (>Needs are remained during starting stage 3mm).Stretching is for big sum Medium sheet material (that is, being multiplied by the size of about 10cm with greater than about 20cm) is needs.

BMG alloy with medium formability needs stretching for most geometries.With the clamping force of 30kN, this A little attainable final sizes of alloy differ markedly from high formability BMG.Big sheet material only can be realized by stretching.Using this Technology described in text, the BMG sheet material for being multiplied by about 10cm size with about 20cm is possible.

BMG alloy with low formation is in T_xHave and be more than 10⁹Pa·s(F<10^-6Pa^-1) viscosity there is low formation And deform during rolling not notable.Therefore, most deformation must occur in drawing process.When including stretching When, preformed thin plate still can be thinning.Using the techniques described herein, the BMG piece of the size of about 3cm is multiplied by with about 20cm Material is possible.

However, having in all wherein BMG raw materials>In the case of the thickness of 3mm, preheating raw material before rolling is Necessary.For raw materials size, for example, after some passages, wherein raw material be with thickness<The sheet of 1mm, by roller Heating can become sufficient and no longer need to preheat.

Another critical aspects of the present invention are accurate temperature and process time control.Accurate temperature control can be by control The temperature of heating element heater processed is realizing.For example, thermocouple feedback can be placed in the group heating roller and for controlling the group heating The temperature of the cartridge heater in roller.In alternatives, temperature control also can be by using the radiant heat on the outside of the group heating roller To realize.Roller also can be heated by submergence in the liquid of heating.Allow accurately other temperature control dresses temperature controlled Put and well known by persons skilled in the art and can be used for the present invention.

As shown in figs. 12, in one embodiment, roller be with by PID- control control resistance heater Heating, wherein thermocouple (being positioned proximate to the surface of roller) is used for measurement temperature.It is highly desirable that in roller surface Temperature homogeneity whole roller large deviations be less than 5 degrees Celsius.

As described above, preheater is the key element of the present invention, because which reducing the formability consumption of BMG.Preheater Requirement be that BMG raw material fully softens so that BMG does not damage roller, adapt to the shape of roller, and while to consume formability minimum Change.

In one embodiment, as shown in Figure 11, preheater can include and heat when raw material is by preheating steps Two heating plates (top and bottom) of raw material.In preheating process, temperature control is crucial, but not in rolling Crucial like that during rolling.Preheater is optionally but it is preferred to have the heating independently of roller and controlling organization.Heating and control The technology of preheater processed can be similar to have been directed towards the technology of roller suggestion.

Preheater shown in Figure 11 allows temperature control in ± 5 degrees Celsius.In an embodiment of the present invention, two add Hot plate is simply by gravity extruding raw material.However, depend on specific BMG type, and the tool of the BMG in the type The property of body and the geometry of BMG raw material, can add extra power.Such power can be adjusted to higher or more as needed Low.

With horizontal sheets of sizes is increased, it can be problematic that BMG adheres to the tendency on roller.BMG must be solved glue Roller is attached to, to keep flatness, thermal conductivity, and continuous formability during whole rotary rolling mill.Raw material adheres to roller On tendency can by compare the driving force (owing to the system energy of the reduction due to adhesiveness) of adhesion and resistance (owing to Strain energy due to the increase of bending) quantify.For Newtonian fluid, as the bending energy of the increase of adhesiveness is shown in equation (4) In:

Wherein λ=3 η is tension force (tension) viscosity of sheet material, and Ω is the angular speed of roller, and I=h₂ ³/ 12 is cross section Rotary inertia.

On the other hand, the adhesion energy of system is shown in equation (5):

U_s=(γ_s-v-γ_s-l) s=(γ_s-v-γ_s-l) R θ=γ_l-vcosβ·Rθ (5)

Wherein β is the contact angle between glassy metal and roller.

Therefore, in order to prevent the adhesion during rolling, it is desirable that:

Or

Adhesion tendency is not also observed for other metals and it is believed that occurs in BMG that (low due to BMG is obtained Viscosity or corresponding flow stress), and therefore, intimate contact between roller and BMG raw material.Therefore, in order to reduce in heat Adhesion during rolling, it is necessary to reduce adhesion energy.

The present invention proposes following strategy to reduce adhesion tendency of the BMG raw material to roller:

(1) reduce microcosmic surface product and observe that adhesion tendency reduces along with very high surface smoothness.Therefore, Attempt to reduce adhesion tendency, roughness reduces.First, adhesion deteriorates, the roughness but being below compared with mirro finished, observation The decline of adhesion is arrived；

(2) surface chemistry is when the roll material with the bad wetting of BMG is selected.Angle of wetting is this means, the β in equation 7 More than 90 degree (equation 7 is always set up).For example, nitride and other ceramic roller surfaces reduce adhesion (increase angle of wetting), and golden Category roller surface promotes adhesion.

(3) related to surface chemistry be BMG raw material oxidation.The oxidized surface of BMG raw material also reduces adhesion.For example, It was found that having the Pt of minimum oxidation tendency_57.5Cu_14.7Ni_5.3P_22.5BMG is most strong to roller adhesion, and Pd₄₃Ni₁₀Cu₂₇P₂₀BMG is adhered to Zr that is notable weaker and being tested₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅There is minimum adhesion tendency in BMG alloy, as shown in Figure 15.

(4) another way for preventing BMG adhesion is to reduce the surface energy of BMG (in equation (7) by adding lubricant γ_1-v).

Figure 15 depicts the Pt of institute's rolling_57.5Cu_14.7Ni_5.3P_22.5The photo of sample.As shown in Figure 15, Pd₄₃Ni₁₀Cu₂₇P₂₀Sample can adhere to top and lower roller simultaneously, and this causes which to tear along center line.

Method described herein allows the ultra-smooth sheet material of block metal glass of the manufacture with low oxidation ratio.

Once additionally, 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) using patterned rolls in BMG sheet material.Such as Shown in Figure 16, the group heating roller rolling is processed and passed through by preheating steps in BMG, then as above retouched in detail After the stretching step that states, BMG can be by one group of follow-up heating roller processing, and one group of follow-up heating roller has and is arranged on which On plane in or the outer pattern of plane so that BMG sheet material patterning.When first group of heating roller is by pattern (plane in or plane outside) When applying to BMG sheet material, the group patterned rolls are maintained at identical or different processing temperature.

These identical patterns also can be molded by using thermoplastic extrusion as shown in Figure 17 or blow molding method To manufacture.In a similar manner, the group heating roller rolling is processed and passed through by preheating steps in BMG, then carry out After stretching step, BMG can stand extrusion molding or blow molding processing, as generally known in the art.The reality of these technology Example is described in, for example, the U.S. Patent number 8 of Schroers et al., the U.S. Patent Publication No. of 641,839 and Schroers et al. In 2013/0306262, its respective theme here is incorporated by with which by quoting.

Additionally, also forming step can be carried out so that block metal glass sheet forming is to mold cavity.If expecting, can carry out Shearing step is to be cut into, by block metal glass sheet material, the profile determined by mold cavity.In another preferred embodiment, Deforming step can be carried out so that block metal glass sheet material wrinkles into the deformity out of plane determined by mold cavity.

By using these methods and other be similarly used for the patterning method of BMG, or even extremely complex shape Spectacle frame for example as shown in Figure 18, it is possible to use method described herein is manufactured.

In another preferred embodiment of the present invention, block metal glass raw material can be included in many of the middle engagement of step b) Individual block metal glass block.As shown in Figure 19, the multiple block metal glass blocks for forming " sandwich " can be connect by rolling Close.The engagement step can be complete, and plurality of block metal glass block is fully engaged without any gap.Substituting Property embodiment in, can control bonding station to prevent several pieces of block metal glass in some engagement position 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 is to prevent block metal glass block in some engagement position in block metal glass block.Can prevent material from connecing in some regions Close so that only block metal glass block in part is that the additive method for engaging is can also be used in the practice of the present 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 Including:

A) one group of pre-add hot plate, wherein the group pre-add hot plate can press from both sides block metal glass raw material in-between with pre-add But hot block metal glass raw material provides to be enough to soften block metal glass raw material significantly disappearing for block metal glass The temperature of the crystallization time of consumption；

B) one group of rotary heating roller of the processing temperature of block metal glass is maintained at, wherein when the group heating roller rotation When, the ground rolling of heating roller thermoplasticity therebetween from pre-add hot plate the step of the block metal glass raw material that receives so that block Glassy metal raw material thinning become block metal glass sheet material；With

As described above, drawing mechanism is moved with respect to negative temperature gradient, wherein when block metal glass is from the group heating roller When drawing or stretching, which is cooled to the temperature of the processing temperature less than BMG.

In one embodiment, drawing mechanism includes the draw-off mechanism of speeds control, wherein when block metal glass piece Material from the group heating roller leave when, speeds control draw-off mechanism drawing block metal glass sheet material.The drawing mechanism preferably with The faster speed of the group heating roller is advanced through than block metal glass and pulls block metal glass sheet material.

In another embodiment, drawing mechanism includes one group of rotatable chill roll.In this embodiment, the group can Rotation chill roll is maintained at than the group heating roller lower temperature and when block metal glass sheet material leaves the group heating roller Receive block metal glass sheet material therebetween.The group chill roll is further preferably with than the faster speed rate rotation of the group heating roller.

Similarly, as described above, after rolling and stretching step, the system of the present invention may additionally include block metal glass piece Pattern is put on after leaving drawing mechanism material one group of rotatable patterned rolls on block metal glass sheet material.In alternatives In, after rolling and stretching step, various processing and forming can be carried out so that pattern is applied on block metal glass sheet material.

In one embodiment, the system of the present invention may include that multiple systems being connected in series are thin continuously to produce Block metal glass sheet material.For example, in addition the system may include the other heating roller of the least one set at multiple stations and least one set Chill roll, wherein block metal glass is thinning further.If desired, one group of preheater plate can be located at least one set other plus Before hot-rolling.If however, block metal glass sheet material is held in enough temperature of rolling between the group heating roller, per Between individual station, preheater plate may not be necessary.As described herein, " cold " roller is only in relation to by group heating roller holding Processing temperature is cold.If block metal glass sheet material is not notable between next subsequent station cooling down, may not be needed Extra preheater step.The best configuration of therefore group preheater plate in system, the group heating roller and the group chill roll can It is determined by those skilled in the art.

The group heating roller optionally includes the face coat on the surface for providing smooth, non-stick thereon.Prevent block gold Category glass adhesion is to heating roller additive method discussed above.Additionally, the group heating roller preferably is contained in block metal glass The sufficiently solid hard metal of processing temperature.

The group chill roll can be with rough surface, so that the group when block metal glass sheet material leaves the group heating roller Block metal glass sheet material kept a firm hand on by chill roll.

Figure 12 and 13 depicts the figure of the preheater plate according to the present invention and the group heating roller.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, preheater plate only can clamp block using gravity Glassy metal raw material optionally provide preheater plate and block metal glass using the instrument of extra offer pressure More intimate contact between raw material.

Servomotor 6 controls the rotation of the group heating roller 8 and 10.Load and displacement transducer 12 can be used to provide to roller The feedback of position.One group of jack screw can be used to control the group to add based on the information received from load and displacement transducer 12 Gap between hot-rolling 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 each also has cartridge heater 20 and passes through them Thermocouple.

Figure 14 depicts the example of the pre-add hot plate 2 and 4 according to the present invention.Measuring scale be in inches.

As described herein, the present invention allows big, thin block metal glass sheet material of the manufacture with uniform thickness.This Outward, the present invention allows block metal glass bar of the manufacture with uniform thickness.The present invention is also allowed in block metal glass sheet material In manufacture further complexity pattern.Additionally, 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 present invention of the block metal glass sheet material of degree and configuration are known to the skilled person and are in In the scope of the present invention.

It should be understood that following claims be intended to cover all of upper and specific features of the present invention described herein and All statements (on language) of the scope of the invention can fall in-between.

Claims

1. the method for manufacturing block metal glass sheet material, the method comprising the steps of:

A) block metal glass raw material is preheated to and is enough to soften block metal glass raw material but block is significantly provided The temperature of the consumption crystallization time of glassy metal；With

B) thermoplasticity preheated piece of the rolling in ground between the one of processing temperature of block metal glass group of heating roller is being maintained at Body glassy metal raw material；

Wherein reduce the thickness of body glassy metal raw material to produce block metal glass sheet material.

2. method according to claim 1, further comprising the steps:

C) the group heating roller after-drawing block metal glass sheet material is left in block metal glass sheet material.

3. method according to claim 1, wherein pre-heating temperature is in about 0.8 times of glass transition of block metal glass raw material Temperature T_gAnd 1.4 times of glass transition temperature between, the glass transition temperature be with degree Celsius measurement.

4. method according to claim 1, wherein in step b) processing temperature of block metal glass be in bulk metal glass Temperature in the supercooling liquid phase region of glass.

5. method according to claim 2, is wherein stretching in negative temperature gradient and occurs.

6. method according to claim 2, wherein stretches and occurs at a controlled rate.

7. method according to claim 2, wherein repeat step a) is to c) to obtain the desired thickness of block metal glass sheet material Degree.

8. method according to claim 1, wherein step a) and b) is carried out in atmosphere.

9. method according to claim 2, wherein step a) is to c) carrying out in atmosphere.

10. method according to claim 1, wherein block metal glass raw material have greater than about 10⁹The viscosity of Pa s, η_min.

11. method according to claim 10, wherein block metal glass raw material have greater than about 10⁷The viscosity of Pa s, η_min.

12. methods according to claim 2, wherein thermoplasticity rolling step reduce thickness disturbance, and which can be in subsequent stretching Increased with magnitude in step process.

13. methods according to claim 2, wherein processing conditions in step a) to being such during c) so that maintainance block The reynolds number Re of body glassy metal<10^-3.

14. methods according to claim 2, wherein mechanical performance are improved by deformation, and the deformation is produced in drawing process Free volume, wherein described block metal glass are changed to extension sexual behaviour from brittle behaviour.

15. methods according to claim 1, wherein block metal glass raw material include multiple block metal glass blocks, wherein institute State the engagement in step b) of multiple block metal glass blocks.

16. methods according to claim 15, wherein control bonding station, and wherein the only part block metal glass block is to connect Close.

17. methods according to claim 2, wherein stretching rolling increased the bend ductility of block metal glass sheet material.

Pattern is put on block metal glass sheet material after further including at step c) by 18. methods according to claim 2 Step.

19. methods according to claim 18, wherein by one group of patterned rolls rolling block metal glass sheet material with by pattern Put on block metal glass sheet material, wherein the group patterned rolls are maintained at the processing temperature of block metal glass sheet material, its Central roll puts on pattern on block metal glass sheet material.

20. methods according to claim 18, wherein after step c), carry out forming step so that pattern is put on bulk metal On glass sheet.

21. methods according to claim 18, wherein after step c), carry out forming step so that block metal glass sheet material becomes Type is to mold cavity.

22. methods according to claim 21, wherein carry out shearing step to cut into block metal glass sheet material by mould The profile that die cavity determines.

23. methods according to claim 21, wherein carry out deforming step so that block metal glass sheet material is wrinkled into by mould The deformity out of plane that die cavity determines.

24. methods according to claim 18, wherein pattern have the length dimension less than 1mm.

25. methods according to claim 24, wherein pattern have the length dimension less than 0.5mm.

26. methods according to claim 18, wherein pattern include mold cavity.

27. make the method that block metal glass deforms, and wherein block metal glass raw material has the thickness less than 0.5mm, described Method is comprised the following steps:

A) thermoplasticity preheated piece of the rolling in ground between the one of processing temperature of block metal glass group of heating roller is being maintained at Body glassy metal raw material；

28. method according to claim 27, further comprising the steps:

B) after block metal glass sheet material leaves the group heating roller, block metal glass sheet material is stretched.

29. make the method that block metal glass deforms, and wherein block metal glass has less than 10⁷Minimal viscosity η of Pa s_min, The method comprising the steps of:

A) temperature of the about 60-100% of processing temperature is preheated to；With

B) it is being maintained between the one of processing temperature of block metal glass group of heating roller, thermoplasticity preheated piece of the rolling in ground Body glassy metal raw material；

The patterned sheet of 30. method manufactures according to claim 1, which has the pattern length size less than 1mm.

The housing of 31. electronic devices, its are formed by the method for claim 18.

The system of 32. manufacture block metal glass sheet materials, the system include:

A) one group of pre-add hot plate, wherein the group pre-add hot plate can clamp therebetween block metal glass raw material to preheat block But glassy metal raw material provides to be enough to soften block metal glass raw material significantly the consumption crystallization of block metal glass The temperature of time；

B) one group of rotary heating roller of the processing temperature of block metal glass is maintained at, wherein when the group heating roller rotates, Heating roller thermoplasticity ground rolling therebetween from pre-add hot plate the step of the block metal glass raw material that receives so that block is golden Category frit thinning become block metal glass sheet material；With

C) drawing mechanism, its can be in the drop-down block metal glass pieces through rolling for extending away from the group heating roller of controlled velocity Material.

33. move along negative temperature gradient according to the system of claim 32, wherein drawing mechanism.

34. according to the system of claim 32, and wherein when drawing mechanism is left from the group heating roller, the drawing mechanism is by speed Degree control.

35. according to the system of claim 34, and wherein drawing mechanism is to be advanced through the group heating roller more than block metal glass Fast speed drawing block metal glass sheet material.

36. include one group of rotatable chill roll according to the system of claim 34, wherein drawing mechanism, and the wherein group is rotatable cold But roller be maintained at than the group heating roller lower temperature and when block metal glass sheet material in-between from the group heating roller from The block metal glass sheet material received when opening.

37. according to the system of claim 34, and wherein drawing mechanism includes clamping device, when block metal glass sheet material is from the group When heating roller leaves, the clamping device receives block metal glass sheet material in-between.

38. according to the system of claim 36, and wherein the group chill roll is with than the faster speed rate rotation of the group heating roller.

39., according to the system of claim 32, further include one group of rotatable patterned rolls, wherein in block metal glass piece After material leaves drawing mechanism, the patterned rolls put on pattern on block metal glass sheet material.

40. are maintained at the processing temperature of block metal glass according to the system of claim 39, wherein group patterned rolls.

41. according to the system of claim 32, and plurality of Cascade System connection, it is possible thereby to obtain thin block metal glass piece Material.

According to the system of claim 32, wherein the group heating roller, 42. include that the surface for providing smooth, non-maxxaedium applies thereon Layer.

43. according to the system of claim 32, and the processing temperature that wherein the group heating roller is included in block metal glass is hard enough Solid hard metal.

44. are carried out in atmosphere according to the system wherein step of claim 32.

45. according to the system of claim 32, including the other chill roll of the other heating roller of least one set and least one set, its In make block metal glass thinning further.

46. according to the system of claim 45, including one group of pre-add hot plate before the other heating roller of least one set.