CN104583435A - Amorphous alloy powder feedstock processing - Google Patents
Amorphous alloy powder feedstock processing Download PDFInfo
- Publication number
- CN104583435A CN104583435A CN201280073303.5A CN201280073303A CN104583435A CN 104583435 A CN104583435 A CN 104583435A CN 201280073303 A CN201280073303 A CN 201280073303A CN 104583435 A CN104583435 A CN 104583435A
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- China
- Prior art keywords
- powder
- bmg
- alloy
- weight
- amorphous
- Prior art date
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- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 97
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title description 61
- 238000000034 method Methods 0.000 claims abstract description 69
- 239000000956 alloy Substances 0.000 claims description 93
- 229910045601 alloy Inorganic materials 0.000 claims description 93
- 239000000203 mixture Substances 0.000 claims description 75
- 239000000463 material Substances 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 20
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- 239000000155 melt Substances 0.000 claims description 14
- 229910052729 chemical element Inorganic materials 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 5
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- 238000001816 cooling Methods 0.000 description 35
- 239000005300 metallic glass Substances 0.000 description 24
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- 238000002425 crystallisation Methods 0.000 description 21
- 230000008025 crystallization Effects 0.000 description 21
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- -1 at least two kinds Chemical class 0.000 description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 3
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- 239000010941 cobalt Substances 0.000 description 3
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- 241000196324 Embryophyta Species 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
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- 229910052702 rhenium Inorganic materials 0.000 description 2
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- 240000006409 Acacia auriculiformis Species 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006291 Si—Nb Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C22C33/00—Making ferrous alloys
- C22C33/003—Making ferrous alloys making amorphous alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/1208—Containers or coating used therefor
- B22F3/1216—Container composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—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
- C22C45/001—Amorphous alloys with Cu 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
- C22C45/003—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
- C22C45/02—Amorphous alloys with iron as the major constituent
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
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Abstract
Described is a method of producing a feedstock comprising a BMG, wherein a powder is compacted to for the feedstock and the powder has elements of the BMG and the elements in the powder have a same weight percentage as in the BMG. Described is a method of producing a feedstock comprising a BMG, wherein a powder is compacted into a sheath to for the feedstock, and the powder and the sheath together have elements of the BMG and the elements in the powder have a same weight percentage as in the BMG.
Description
Background technology
Most of metal alloy of current use is at least initial all by solidifying casting to process.Metal alloy melts and waters and casts from metal or ceramic die, and solidifies wherein.Peel off mould, and casting metals part is ready to for use or processes further.Rate of cooling is depended at the as-cast structure of most of material of solidification and cooling period generation.The character of change does not have general rule, but for most of parts, structure only little by little changes along with rate of cooling change.On the other hand, for bulk-solidification type amorphous alloy, cooling and change between crystalline state that the metamict that produces and relatively slow cooling produce is the change of matter but not the change (these two states have different characteristics) of amount relatively fast.
Bulk-solidification type amorphous alloy or block metal glass (" BMG ") are a metalloid material of exploitation recently.These alloys relatively slow speed can solidify and cool, and they at room temperature keep unbodied noncrystalline (that is, vitreous state) state.This metamict can be very favorable for some application.But if rate of cooling is fast not, then crystal may during cooling be formed at alloy inside, makes the beneficial effect of metamict partly or entirely lose.Such as, the risk manufacturing bulk amorphous alloys parts is because in Slow cooling or starting material, the reason of impurity causes local-crystalized.
In various metals system, prepare bulk-solidification type amorphous alloy.They are usually by from being quenched to envrionment temperature to be prepared higher than melt temperature.In general, the such as order of magnitude is needed to be 10
5dEG C/sec high rate of cooling realize amorphous structure.Bulk-solidification type alloy can be made to cool to avoid crystallization, thus during cooling realize and keep the dead slow of amorphous structure, this dead slow is called " critical cooling rate " of alloy.In order to realize the rate of cooling higher than critical cooling rate, heat must be extracted from sample.Therefore, the thickness of the article manufactured from amorphous alloy usually becomes restricted yardstick, is generally referred to as " critical (casting) thickness ".Can be calculated by hot-fluid, consider critical cooling velocity, obtain the critical thickness of amorphous alloy.
Until the early 1990s, the workability of amorphous alloy is still quite limited, and amorphous alloy is only easy in powder form or be less than the very thin paper tinsel of 100 microns with critical thickness or bar obtains.Develop in the nineties a kind of mainly based on the amorphous alloy of Zr and Ti alloy system, and have developed more amorphous alloy systems based on different element since then.These alloy families have and are less than 10
3dEG C/sec much lower critical cooling rate, thus they have critical casting thickness much bigger compared with the counterpart before it.But, but seldom mention about how to utilize these alloy systems and/or be shaped to construction package (those construction packages in such as consumer-elcetronics devices).Specifically, when the large product (as steel plate) of long-width ratio of touching upon or three-dimensional hollow product, the formation existed or treatment process usually cause product cost high.In addition, the method existed usually may have product manufacturing shortcoming, and namely product loses the mechanical property desired by much observing in amorphous alloy.
Summary of the invention
A kind of method preparing the feed comprising BMG is described herein.Powder is pressed to form feed.Powder has the element of BMG, and these elements in powder have the weight percent identical with BMG.
A kind of method preparing the feed comprising BMG is described herein.Powder is pressed in jacket to form feed.Powder has the element of BMG together with jacket, and these elements in powder have the weight percent identical with BMG.
Accompanying drawing explanation
Fig. 1 provides a kind of Temperature-Viscosity figure of exemplary block coagulating type amorphous alloy.
Fig. 2 provides the schematic diagram of Time-temperature-transformation (T) figure for a kind of exemplary block coagulating type amorphous alloy.
Fig. 3 shows the schematic diagram of pressed powder.
Fig. 4 shows powder compression to the schematic diagram in jacket.
Embodiment
The all publications quoted in this manual, patent and patent application are incorporated to way of reference all accordingly in full.
Article used herein " one " and " one " refer to the grammar object of one or more than one (that is, at least one) article.By way of example, " fluoropolymer resin " means a kind of fluoropolymer resin or more than a kind of fluoropolymer resin.Any scope quoted herein includes end value interior.Term " substantially " used in the full text of this specification sheets and " about " are for describing and little fluctuation being described.Such as, they can refer to be less than or equal to ± and 5%, be such as less than or equal to ± 2%, be such as less than or equal to ± 1%, be such as less than or equal to ± 0.5%, be such as less than or equal to ± 0.2%, be such as less than or equal to ± 0.1%, be such as less than or equal to ± 0.05%.
Bulk-solidification type amorphous alloy or block metal glass (" BMG ") are a metalloid material of exploitation recently.These alloys relatively slow speed can solidify and cool, and they at room temperature keep unbodied noncrystalline (that is, vitreous state) state.Amorphous alloy has many attributes more superior than its crystalline state counterpart.But if rate of cooling is fast not, then crystal may during cooling be formed at alloy inside, makes the beneficial effect of metamict to lose.Such as, the challenge manufacturing bulk amorphous alloys parts is the local-crystalized of the parts caused by the impurity in Slow cooling or alloy raw material.Owing to expecting the amorphicity (on the contrary, the degree of crystallinity compared with low degree) of higher degree in BMG parts, therefore need the method for the BMG parts developed for casting the amorphicity with controlled quatity.
Fig. 1 (deriving from United States Patent (USP) 7,575,040) shows the temperature-viscosity curve figure of an exemplary block coagulating type amorphous alloy of the Zr--Ti--Ni--Cu--Be race VIT-001 series that free Liquidmetal Technology manufactures.It should be pointed out that during formation amorphous solid, the obvious liquid/solid that there is not bulk-solidification type amorphous metal changes.Along with overcooling expands gradually, the alloy of melting becomes more and more sticky, until its at about second-order transition temperature place close to solid form.Therefore, the temperature of the solidified front of bulk-solidification type amorphous alloy can be about second-order transition temperature, and wherein for the object of the amorphous plate section product extracted through quenching, in fact alloy will serve as solid.
Fig. 2 (deriving from United States Patent (USP) 7,575,040) shows a kind of Time-temperature-transformation (TTT) cooling curve or TTT figure of exemplary block coagulating type amorphous alloy.The same with common metal, bulk-solidification type amorphous metal can not experience liquid/solid crystalline transition when cooling.On the contrary, along with temperature reduces (close to glass transition temperature Tg), the metal of the non-crystalline state form of the height fluid found under high temperature (close to " melt temperature " Tm) becomes more tacky, finally presents the external physical property of Conventional solid.
Although bulk-solidification type amorphous metal does not exist liquid/crystalline transition, " melt temperature " Tm can be defined as the thermodynamics liquidus temperature of corresponding crystallization phases.Under this system, the viscosity of the bulk-solidification type amorphous alloy under melt temperature can be in about 0.1 pool in the scope of about 10,000 pool, and even sometimes lower than 0.01 pool.Being undertaken providing the complicated fine portion of use bulk-solidification type amorphous metal to housing/mould sooner and filling completely compared with low viscosity, for formation BMG parts under " melt temperature ".In addition, the rate of cooling of molten metal formation BMG parts should make during cooling time temperature curve not be horizontally through the nose shape region of the crystallizing field defined in the TTT figure of Fig. 2.In fig. 2, Tnose be wherein crystallization the most rapidly and the critical crystal temperature Tx occurred in shortest time yardstick.
Supercooling liquid phase region (humidity province between Tg and Tx) is the embodiment of the remarkable stability of the crystallization stoping block coagulating type alloy.In this humidity province, bulk-solidification type alloy can be used as highly viscous liquid and exists.The viscosity of bulk-solidification type alloy in supercooling liquid phase region can under second-order transition temperature 10
12under Pas and Tc (high temperature limit of supercooling liquid phase region) 10
5change between Pas.The liquid with this viscosity can stand basic plastix strain under an applied pressure.Embodiment herein uses the larger plastic formability in supercooling liquid phase region as being shaped and separation method.
Need to carry out some explainations to Tx.Technically, Tx is described as the function of temperature and time by the nose sigmoid curve shown in TTT figure.Therefore, which kind of path no matter taked when heating or cool metal alloy is, when encountering TTT curve, just reaches Tx.Tx in fig. 2, Tx is depicted as dotted line, because can be changed to close to Tg from close to Tm.
The schematic TTT of Fig. 2 illustrates when Time-temperature path (being depicted as (1), as an exemplary path) does not encounter TTT curve, from be in or higher than Tm to the die-casting process method lower than Tg.During die casting, being shaped and cooling fast occurs substantially simultaneously, encounters TTT curve to avoid path.((2), (3) and (4) are depicted as at Time-temperature path, exemplarily property path) when not encountering TTT curve, from be in or lower than Tg to superplastic forming (SPF) working method lower than Tm.In SPF, amorphous BMG is reheated to supercooling liquid phase region, in this supercooling liquid phase region can process window may than much bigger during die casting, thus cause technique to possess better controllability.SPF technique does not need cooling fast to avoid during cooling crystallization.In addition, as shown in exemplary path (2), (3) and (4), SPF can top temperature during SPF higher than Tnose or lower than Tnose, be up to about Tm carry out.If heat an amorphous alloy but manage to avoid encountering TTT curve, be then heated to " between Tg and Tm ", but can not Tx be reached.
Typical difference scanning calorimeter instrument (DSC) heating curve of the bulk-solidification type amorphous alloy obtained under the heating rate of 20 DEG C/min essentially describes the specific path across TTT data, wherein may see the Tg at certain temperature, heat slope across Tx during TTT crystallization starting point and when same path is across final melting peak when being used for the temperature range of melting as DSC.If heat block coagulating type amorphous alloy with the fast heating rate shown in the inclination heating-up section of the path (2) in such as Fig. 2, (3) and (4), then may avoid TTT curve completely, and DSC data are by glass transition when heating is shown but without Tx.Consider that the another kind of mode of this process is, as long as path (2), (3) and (4) do not encounter crystallization curve, these paths just can drop on any position between the nose (and even higher than this place) of TTT curve and Tg line in temperature.This only means that the levelling bench in path significantly may shorten along with the raising of processing temperature.
phase
Term " phase " herein can refer to the phase found in thermodynamics phasor.Mutually for all physical propertys throughout wherein material are consistent space (as thermodynamical system) region substantially.The example of physical property comprises density, specific refractory power, chemical constitution and lattice period.By be described as simply mutually chemically unanimously, different physically and/or can the region of material of mechanical separation.Such as, be in the system be made up of ice and water in glass pot, ice cube is a phase, and water is second-phase, and the wet air of side waterborne is third phase.The glass of tank is separated phase for another.Can refer to sosoloid mutually, this sosoloid can be solution or compound, the such as intermetallics of binary, ternary, quaternary or more unit.And for example, amorphous phase is different from crystallization phases.
metal, transition metal and nonmetal
Term " metal " refers to electropositive chemical element.Term " element " in this specification sheets typically refers to the element be found in the periodic table of elements.Physically, the atoms metal in ground state comprises the band be partially filled of the empty state had close to occupied state.Term " transition metal " is in the periodic table of elements, the 3rd race is to any metallic element in the 12nd race, and it has incomplete inner shell, and in series of elements, play the effect of transition connection between maximum positive polarity and minimum positive polarity.Transition metal is characterized by multiple valency, coloured compound and the ability that forms stable complex ion.Term " nonmetal " refers to the chemical element not having and lose electronics and form cation capacity.
Depend on application, any suitable non-metallic element or their combination can be used.Alloy (or " alloy composite ") can comprise multiple non-metallic element, such as at least two kinds, at least three kinds, at least four kinds, or more plant non-metallic element.Non-metallic element can be any element seen in the periodic table of elements in 13-17 race.Such as, non-metallic element can be any one in F, Cl, Br, I, At, O, S, Se, Te, Po, N, P, As, Sb, Bi, C, Si, Ge, Sn, Pb and B.Sometimes, non-metallic element also can refer to some metalloid (such as, B, Si, Ge, As, Sb, Te and Po) in 13-17 race.In one embodiment, non-metallic element can comprise B, Si, C, P or their combination.Therefore, such as, alloy can comprise boride, carbide or both.
Transition metal can be scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury,
(rutherfordium),
(dubnium),
(seaborgium), beryllium (bohrium),
(hassium),
(meitnerium),
(ununnilium),
(unununium) and
(ununbium) any one in.In one embodiment, the BMG comprising transition metal can have at least one in Sc, Y, La, Ac, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg.Depend on application, any suitable transition metal or their combination can be used.This alloy composite can comprise multiple transition metal, such as at least two kinds, at least three kinds, at least four kinds, or more plant transition metal.
Current described alloy or alloy " sample " or " sample " alloy can have any shape or size.Such as, described alloy can have particulate form, and this particulate form can have such as spherical, ellipsoid shape, wire, shaft-like, sheet, flake or erose shape.Described particulate can have any size.Such as, it can have the mean diameter between about 1 micron and about 100 microns, such as between about 5 microns and about 80 microns, such as between about 10 microns and about 60 microns, such as between about 15 microns and about 50 microns, such as between about 15 microns and about 45 microns, such as between about 20 microns and about 40 microns, such as between about 25 microns and about 35 microns.Such as, in one embodiment, the mean diameter of particulate is between about 25 microns and about 44 microns.In certain embodiments, those particulates in less particulate such as nanometer range can be used, or larger particulate is such as greater than those particulates of 100 microns.
Alloy sample or sample can also have much bigger yardstick.Such as, it can be block structure assembly, the shell/protective sleeve of such as ingot bar, electronics or or even have millimeter, centimetre or meter within the scope of the part of construction package of size.
sosoloid
Term " sosoloid " refers to the solution of solid form.Term " solution " refers to the mixture of two or more materials, and it can be solid, liquid, gas or these combination.This mixture can be homogeneous or heterogeneous.Term " mixture " is the composition of two or more materials being bonded to each other and usually can being separated.In general, these two or more materials not mutual chemical combination.
alloy
In certain embodiments, alloy composite described herein can by complete alloying.In one embodiment, term " alloy " refers to homogenizing mixture or the sosoloid of two or more metals, and wherein a kind of atom of metal replaces or occupies the interstitial site between the atom of another metal; Such as, brass is the alloy of zinc and copper.Different from mixture, alloy can refer to the sosoloid partially or completely of one or more elements in metallic matrix, one or more compounds in such as metallic matrix.Term alloy herein can refer to can provide the complete solid solution alloy of single solid phase microstructure and can provide both part solutions of two or more phases.Alloy composite described herein can refer to the alloy composite comprising alloy, or comprises the alloy composite of the mixture containing alloy.
Therefore, the alloy of complete alloying can have equally distributed composition, be no matter solid solution phase, Compound Phase or both.Subtle change in term as used herein " complete alloying " soluble error margin.Such as, it can refer at least 90% alloying, such as at least 95% alloying, such as at least 99% alloying, such as at least 99.5% alloying, such as at least 99.9% alloying.Per-cent herein can refer to volume percent or weight percent, and this depends on context.These per-cents can be balanced by impurity, and it may not be a part for alloy in composition or phase.
amorphous or non-crystalline solids
" amorphous " or " non-crystalline solids " lacks the solid as the lattice period of crystal property.As used herein, " amorphous solid " comprises " glass ", and it to be softened by glass transition when heating and is transformed into the amorphous solid of class I liquid I state.In general, although amorphous material can have some short range orders because of the character of chemical bonding under atomic length yardstick, they lack the long-range order characteristic of crystal.Based on by the determined lattice period of structural characterization technology such as X-ray diffraction and transmission electron microscopy, amorphous solid and crystalline solid can be distinguished.
Term " in order " and " unordered " specify the presence or absence of some symmetry or dependency in many-particle system.It is orderly that term " long-range order " and " short range order " are distinguished in material based on length dimension.
In solid, most precise form is lattice period in order: repeatedly repeat certain pattern (atomic arrangement in structure cell) to form translation invariant space splicing (tiling).This is the bounded attribute of crystal.Possible symmetry is divided into 14 Bradley phenanthrene (Bravais) lattices and 230 spacers.
Lattice period means long-range order.If only a known structure cell, then can predict all atom sites in any distance exactly by translational symmetry.Normally correct conversely, except such as there is the splicing of perfect determinacy but not having in the quasicrystal of lattice period.
Long-range order characterizes the physical system of the remote part performance related behavior of wherein same sample.This can be expressed as relevance function, i.e. spin-spin relevance function: G (x, x ')=<s (x), s (x ') >.
In superincumbent function, s is spin quantum number, and x is the distance function in concrete system.As x=x', this function equals 1, and along with distance | x-x'| increases and reduces.Usually, it exponentially decays to zero in larger distance, and thinks that this system is unordered.But, if relevance function is large | x-x'| place decays to constant value, then can think that this system has long-range order.If its power as distance decays to zero, then it can be called as accurate long-range order.Note, so-called formation | the large numerical value of x-x'| is relative.
When some parameters defining its behavior are the stochastic variable do not developed in time, can think that system presents quenching unordered (namely they are quenchings or freezing), as spin glass.This is unordered contrary with annealing, allows oneself to develop in the unordered middle stochastic variable of this annealing.Embodiment herein comprises and comprises the unordered system of quenching.
Alloy as herein described can be crystalline state, partiallycrystalline states, amorphous or essentially no setting.Such as, alloy sample/sample can comprise at least some degree of crystallinity, and wherein crystal grain/crystal has the size be in nanometer and/or micrometer range.Alternatively, alloy can be substantially unbodied, such as completely unbodied.In one embodiment, alloy composite is not unbodied at least substantially, be such as substantially crystalline state, such as complete crystalline state.
In one embodiment, crystal or the existence of multiple crystal in other amorphous alloy can be regarded as " crystallization phases " wherein.The degree of crystallinity (or in certain embodiments referred to as " degree of crystallinity ") of alloy can refer to the amount of the crystallization phases be present in alloy.Described degree can refer to the mark of the crystal be such as present in alloy.Based on context, described mark can refer to volume fraction or weight fraction.Can be amorphicity to the measuring of " amorphous " of amorphous alloy.Amorphicity can be measured according to the degree of degree of crystallinity.Such as, in one embodiment, the alloy with the degree of crystallinity of low degree can be considered to have the amorphicity of high level.In one embodiment, such as, the alloy with the crystallization phases of 60 volume % can have the amorphous phase of 40 volume %.
amorphous alloy or amorphous metal
" amorphous alloy " is greater than the amorphous content of 50 volume % for having, be preferably greater than the amorphous content of 90 volume %, more preferably greater than 95 volume % amorphous content and be most preferably greater than the alloy of 99 volume % to the almost amorphous content of 100 volume %.Note, as mentioned above, the amorphicity of alloy is high, and to be equivalent to degree of crystallinity low." amorphous metal " is for having the amorphous metallic material of unordered atomicscale structure.With for crystalline state and compared with the most metals therefore with the atomic arrangement of high-sequential, amorphous alloy is amorphous.During cooling the direct material producing such disordered structure from liquid state is sometimes referred to as " glass ".Therefore, usually amorphous metal is called " metallic glass " or " glassy metal ".In one embodiment, block metal glass (" BMG ") can refer to alloy, and its microstructure is unbodied at least partly.But except cooling extremely fast, also there is many modes to produce amorphous metal, these modes comprise physical vapor deposition, solid state reaction, ion irradiation, melt-spinning and mechanical alloying.No matter how amorphous alloy is prepared, and they may be unitary class material.
Amorphous metal is prepared by multiple method for rapid cooling.Such as, amorphous metal is produced by being splashed to by molten metal on rotating metallic dish.The quick cooling per second of about degree up to a million can be too fast and can not form crystallization, and therefore by material " locking " in vitreousness.In addition, can be low the critical cooling rate that is enough to allow amorphous structure to be formed in the mode of thick-layer to prepare amorphous metal/alloy, as block metal glass.
Term " block metal glass " (" BMG "), bulk amorphous alloys (" BAA ") and bulk-solidification type amorphous alloy use in this article interchangeably.They refer to the amorphous alloy of the minimum size had at least within the scope of millimeter.Such as, described size can be at least about 0.5mm, such as at least about 1mm, such as at least about 2mm, such as at least about 4mm, such as at least about 5mm, such as at least about 6mm, such as at least about 8mm, such as at least about 10mm, such as at least about 12mm.Depend on geometrical shape, described size can refer to diameter, radius, thickness, width, length etc.BMG also can be to have in cm range such as at least about 1.0cm, such as at least about 2.0cm, such as at least about 5.0cm, such as at least about the metallic glass of at least one size of 10.0cm.In certain embodiments, BMG can have at least one size at least within the scope of rice.BMG can present the above-mentioned any shape relevant with metallic glass or form.Therefore, in certain embodiments, BMG as herein described can be different from an importance that the film made by conventional deposition technique-the former can have the size more much bigger than the latter.
Amorphous metal can be alloy, instead of pure metal.This alloy can comprise the atom of obvious different size, thus causes the low free volume in molten state (and therefore having the viscosity reaching several order of magnitude than other metals and alloy height).This viscosity prevents atom fully mobile to form orderly lattice.Material structure can cause the low-shrinkage of cooling period and the resistivity to viscous deformation.There is not the better resistivity that the crystal boundary weakness of crystalline material (in some cases for) can such as cause abrasion and corrosion.In one embodiment, amorphous metal (say technically as glass) simultaneously also comparable oxide glass and pottery tough and tensile more than and non-friable.
The thermal conductivity of amorphous material can lower than the thermal conductivity of its crystalline state counterpart.Even if form amorphous structure to still realize during comparatively Slow cooling, this alloy can be made up of three kinds or more kind component, thus causes having the crystal unit of the complexity compared with high potential energy and lower formation probability.The formation of amorphous alloy can be depending on multiple factor: the composition of the component of alloy; The atomic radius of component (preferably have significant difference to obtain high-bulk-density and low free volume) more than 12%; And blending ingredients combines, suppresses crystal nucleation and extend the negative heat that molten metal is in the time of overcooling state.But, because the formation of amorphous alloy is based on much different variablees, therefore may be difficult to determine whether alloy composite will form amorphous alloy in advance.
Such as, the amorphous alloy with boron, silicon, phosphorus and other glass formers of magneticmetal (iron, cobalt, nickel) can be magnetic, has low Coercive Force and high resistance.High resistance causes the low-loss when standing alternating magnetic field caused by eddy current, such as, as the useful attribute of magnetic core of transformer.
Amorphous alloy can have the characteristic of multiple potentially useful.Particularly, they tend to stronger than the crystal alloy of similar chemical constitution, and they can bear reversible (" elasticity ") distortion larger than crystal alloy.The intensity of amorphous metal directly comes from their amorphous structure, and described amorphous structure may not have any defect (such as dislocation) of the intensity of restriction crystal alloy.Such as, a kind of modern amorphous metal, is called as Vitreloy
tM, there is the tensile strength of the tensile strength twice being almost senior titanium.In certain embodiments, the metallic glass under room temperature is not ductile and tends to sudden failure when loading under stressing conditions, which has limited the suitability of the material in the application focusing on reliability, because imminent inefficacy is unconspicuous.
Therefore, in order to defeat this challenge, the metal matrix composite material having and comprise the dendrite particle of ductile amorphous metal or the metallic glass matrix of fiber can be used.Alternatively, the BMG tending to cause brittle one or more elements (as Ni) content low can be used.Such as, not can be used for containing the BMG of Ni the ductility improving BMG.
The characteristic that the another kind of bulk amorphous alloys is useful is that they can be true glass; In other words, they can soften when heating and flow.This just can allow easily to process in the mode almost identical with polymkeric substance, such as passes through injection moulding.Therefore, amorphous alloy can be used to prepare athletic equipment, medical facilities, electronic package and equipment and film.Can via the film of high-velocity oxy-fuel deposition techniques amorphous metal as protective coating.
Material can have amorphous phase, crystallization phases or they both.Amorphous phase and crystallization phases can have identical chemical constitution and only different in microstructure, and namely one is amorphous microstructure and another one is crystalline microstructure.Microstructure in one embodiment refers to by microscope with 25 x magnifications or the more structure of material that shows of high power.Alternatively, these two phases can have different chemical constitutions and microstructure.Such as, composition can be part amorphous, substantially unbodied or completely unbodied.
As mentioned above, by the crystalline fraction that exists in alloy to measure the degree (otherwise and for degree of degree of crystallinity) of amorphicity.This degree can refer to volume fraction or the weight fraction of the crystallization phases be present in alloy.Part amorphous composition can refer to that it is at least about 5 volume %, such as at least about 10 volume %, such as at least about 20 volume %, such as at least about 40 volume %, such as at least about 60 volume %, such as at least about 80 volume %, be such as the composition of amorphous phase at least about 90 volume %.Define term " substantially " and " about " at the elsewhere of the application.Therefore, at least substantially, unbodied composition can refer to that it is at least about 90 volume %, such as at least about 95 volume %, such as at least about 98 volume %, such as at least about 99 volume %, such as at least about 99.5 volume %, such as at least about 99.8 volume %, be such as unbodied composition at least about 99.9 volume %.In one embodiment, unbodied composition can have the crystallization phases of some the subsidiary trace existed wherein substantially.
In one embodiment, for amorphous phase, amorphous alloy composition can be homogeneous.On composition, uniform material is homogeneous.This contrasts with for heterogeneous material is formed.Term " composition " refers to chemical constitution in material and/or microstructure.When being split into two halves by the material of certain volume and two halves all have substantially the same composition, this material is homogeneous.Such as, when the microparticle suspending liquid of certain volume is split into two halves and two halves all have the particle of substantially the same volume, this microparticle suspending liquid is homogeneous.But, independent particle may be seen under the microscope.Another example of homogeneous substance is air, although particle wherein in air, gas can be analyzed with liquid separately or be separated from air, heterogeneity equal probability ground wherein suspends.
The composition being homogeneous for amorphous alloy can refer to the composition with equally distributed amorphous phase substantially in its whole microstructure.In other words, said composition to be macroscopically included in whole composition equally distributed amorphous alloy substantially.In the embodiment of alternative, said composition can be mixture, and this mixture has the amorphous phase with non-amorphous phase wherein.This non-amorphous can be a kind of crystal or multiple crystal mutually.This crystal can be any shape such as spherical, ellipsoid shape, wire, shaft-like, sheet, flake or erose particulate form.In one embodiment, it can have dendritic form.Such as, unbodied composite composition can have the crystallization phases of the dendrite shape be scattered in amorphous phase matrix at least in part; This dispersion can be even or heterogeneous, and this amorphous phase and crystallization phases can have identical or different chemical constitution.In one embodiment, they have substantially the same chemical constitution.In another embodiment, the comparable BMG phase of crystallization phases more easily extends.
Method described herein can be applicable to the amorphous alloy of any type.Similarly, herein as composition or goods composition described by amorphous alloy can be any type.Amorphous alloy can containing element Zr, Hf, Ti, Cu, Ni, Pt, Pd, Fe, Mg, Au, La, Ag, Al, Mo, Nb, Be or their combination.That is, alloy can comprise the arbitrary combination of these elements at its chemical formula or chemical constitution.Described element can be different weight or meausurement per-cent and exist.Such as, the iron that iron " base " alloy can refer to have non-slight weight percent is present in alloy wherein, this weight percent can be such as at least about 20 % by weight, such as at least about 40 % by weight, such as at least about 50 % by weight, such as at least about 60 % by weight, such as at least about 80 % by weight.Alternatively, in one embodiment, above-mentioned per-cent can be volume percent, instead of weight percent.Therefore, amorphous alloy can be zirconium base, titanium base, platinum base, palladium base, auri, money base, copper base, iron-based, Ni-based, aluminium base, molybdenum base etc.This alloy can not also contain any one in aforementioned elements, with applicable specific purpose.Such as, in certain embodiments, this alloy or the composition that comprises this alloy can be substantially free of nickel, aluminium, titanium, beryllium or their combination.In one embodiment, this alloy or mixture completely not nickeliferous, aluminium, titanium, beryllium or their combination.
Such as, amorphous alloy can have formula (Zr, Ti)
a(Ni, Cu, Fe)
b(Be, Al, Si, B)
c, wherein a, b and c represent weight or atomic percent separately.In one embodiment, with atomic percentage, a is in the scope of 30 to 75, and b is in the scope of 5 to 60, and c is in the scope of 0 to 50.Alternatively, amorphous alloy can have formula (Zr, Ti)
a(Ni, Cu)
b(Be)
c, wherein a, b and c represent weight or atomic percent separately.In one embodiment, with atomic percentage, a is in the scope of 40 to 75, and b is in the scope of 5 to 50, and c is in the scope of 5 to 50.This alloy can also have formula (Zr, Ti)
a(Ni, Cu)
b(Be)
c, wherein a, b and c represent weight or atomic percent separately.In one embodiment, with atomic percentage, a is in the scope of 45 to 65, and b is in the scope of 7.5 to 35, and c is in the scope of 10 to 37.5.Alternatively, alloy can have formula (Zr)
a(Nb, Ti)
b(Ni, Cu)
c(Al)
d, wherein a, b, c and d represent weight or atomic percent separately.In one embodiment, with atomic percentage, a is in the scope of 45 to 65, and b is in the scope of 0 to 10, and c is in the scope of 20 to 40, and d is in the scope of 7.5 to 15.An exemplary embodiment of aforementioned alloy system is by Liquidmetal Technologies, and the commodity that CA, USA manufacture are called Vitreloy
tMthe Zr-Ti-Ni-Cu-Be base amorphous alloy of (such as Vitreloy-1 and Vitreloy-101).Some examples of the amorphous alloy of different system are provided in table 1 and table 2.
table 1: exemplary amorphous alloy composition
Alloy | Atom % | Atom % | Atom % | Atom % | Atom % | Atom % | Atom % | Atom % |
1 | Fe | Mo | Ni | Cr | P | C | B | |
68.00% | 5.00% | 5.00% | 2.00% | 12.50% | 5.00% | 2.50% | ||
2 | Fe | Mo | Ni | Cr | P | C | B | Si |
68.00% | 5.00% | 5.00% | 2.00% | 11.00% | 5.00% | 2.50% | 1.50% | |
3 | Pd | Cu | Co | P | ||||
44.48% | 32.35% | 4.05% | 19.11% | |||||
4 | Pd | Ag | Si | P | ||||
77.50% | 6.00% | 9.00% | 7.50% | |||||
5 | Pd | Ag | Si | P | Ge | |||
79.00% | 3.50% | 9.50% | 6.00% | 2.00% | ||||
6 | Pt | Cu | Ag | P | B | Si | ||
74.70% | 1.50% | 0.30% | 18.0% | 4.00% | 1.50% |
table 2: additional exemplary amorphous alloy composition (atom %)
Alloy | Atom % | Atom % | Atom % | Atom % | Atom % | Atom % |
1 | Zr | Ti | Cu | Ni | Be | |
41.20% | 13.80% | 12.50% | 10.00% | 22.50% | ||
2 | Zr | Ti | Cu | Ni | Be | |
44.00% | 11.00% | 10.00% | 10.00% | 25.00% | ||
3 | Zr | Ti | Cu | Ni | Nb | Be |
56.25% | 11.25% | 6.88% | 5.63% | 7.50% | 12.50% | |
4 | Zr | Ti | Cu | Ni | Al | Be |
64.75% | 5.60% | 14.90% | 11.15% | 2.60% | 1.00% | |
5 | Zr | Ti | Cu | Ni | Al | |
52.50% | 5.00% | 17.90% | 14.60% | 10.00% | ||
6 | Zr | Nb | Cu | Ni | Al | |
57.00% | 5.00% | 15.40% | 12.60% | 10.00% | ||
7 | Zr | Cu | Ni | Al | ||
50.75% | 36.23% | 4.03% | 9.00% | |||
8 | Zr | Ti | Cu | Ni | Be | |
46.75% | 8.25% | 7.50% | 10.00% | 27.50% | ||
9 | Zr | Ti | Ni | Be | ||
21.67% | 43.33% | 7.50% | 27.50% | |||
10 | Zr | Ti | Cu | Be | ||
35.00% | 30.00% | 7.50% | 27.50% | |||
11 | Zr | Ti | Co | Be | ||
35.00% | 30.00% | 6.00% | 29.00% | |||
12 | Zr | Ti | Fe | Be | ||
35.00% | 30.00% | 2.00% | 33.00% | |||
13 | Au | Ag | Pd | Cu | Si | |
49.00% | 5.50% | 2.30% | 26.90% | 16.30% | ||
14 | Au | Ag | Pd | Cu | Si |
50.90% | 3.00% | 2.30% | 27.80% | 16.00% | ||
15 | Pt | Cu | Ni | P | ||
57.50% | 14.70% | 5.30% | 22.50% | |||
16 | Zr | Ti | Nb | Cu | Be | |
36.60% | 31.40% | 7.00% | 5.90% | 19.10% | ||
17 | Zr | Ti | Nb | Cu | Be | |
38.30% | 32.90% | 7.30% | 6.20% | 15.30% | ||
18 | Zr | Ti | Nb | Cu | Be | |
39.60% | 33.90% | 7.60% | 6.40% | 12.50% | ||
19 | Cu | Ti | Zr | Ni | ||
47.00% | 34.00% | 11.00% | 8.00% | |||
20 | Zr | Co | Al | |||
55.00% | 25.00% | 20.00% |
Other exemplary ferrous metal base alloys comprise composition, disclosed those in such as U.S. Patent Application Publication No.2007/0079907 and No.2008/0118387.These compositions comprise Fe (Mn, Co, Ni, Cu) (C, Si, B, P, Al) system, wherein Fe content is 60 to 75 atomic percents, (Mn, Co, Ni, Cu) total amount in 5 to 25 atomic percent range, and (C, Si, B, P, Al) total amount in 8 to 20 atomic percent range, and comprise exemplary composition Fe48Cr15Mo14Y2C15B6.They also comprise by Fe-Cr-Mo-(Y, Ln)-C-B, Co-Cr-Mo-Ln-C-B, Fe-Mn-Cr-Mo-(Y, Ln)-C-B, (Fe, Cr, Co)-(Mo, Mn)-(C, B)-Y, Fe-(Co, Ni)-(Zr, Nb, Ta)-(Mo, W)-B, Fe-(Al, Ga)-(P, C, B, Si, Ge), Fe-(Co, Cr, Mo, Ga, Sb)-P-B-C, (Fe, Co)-B-Si-Nb alloy and Fe-(Cr-Mo)-(C, B) alloy system described in-Tm, wherein Ln represents lanthanon and Tm represents transition metal.In addition, amorphous alloy can also be the one in exemplary composition Fe80P12.5C5B2.5, Fe80P11C5B2.5Si1.5, Fe74.5Mo5.5P12.5C5B2.5, Fe74.5Mo5.5P11C5B2.5Si1.5, Fe70Mo5Ni5P12.5C5B2.5, Fe70Mo5Ni5P11C5B2.5Si1.5, Fe68Mo5Ni5Cr2P12.5C5B2.5 and Fe68Mo5Ni5Cr2P11C5B2.5Si1.5, as described in U.S. Patent Application Publication No.2010/0300148.
Amorphous alloy also can be ferrous alloy, such as (Fe, Ni, Co) base alloy.The example of such composition at United States Patent (USP) 6,325,868, No.5,288,344, No.5,368,659, No.5,618,359 and No.5, the people such as 735,975, Inoue, Appl.Phys.Lett., the 71st volume, the 464th page (1997), the people such as Shen, Mater.Trans., JIM, 42nd volume, the 2136th page (2001), and disclosed in having in Japanese patent application No.200126277 (publication number 2001303218A).A kind of exemplary composition is Fe
72al
5ga
2p
11c
6b
4.Another example is Fe
72al
7zr
10mo
5w
2b
15.The another kind of ferrous alloy system that can be used in this paper coating is disclosed in U.S. Patent Application Publication No.2010/0084052, wherein amorphous metal comprises such as manganese (1 to 3 atom %), yttrium (0.1 to 10 atom %) and silicon (0.3 to 3.1 atom %), and compositing range provides in bracket; And comprise following element: chromium (15 to 20 atom %), molybdenum (2 to 15 atom %), tungsten (1 to 3 atom %), boron (5 to 16 atom %), carbon (3 to 16 atom %), and surplus is iron, the compositing range of specifying provides in bracket.
Aforesaid amorphous alloy system also can comprise additional element, and such as additional transition metal, comprises Nb, Cr, V and Co.Described additional element can be less than or equal to about 30 % by weight, be such as less than or equal to about 20 % by weight, be such as less than or equal to about 10 % by weight, be such as less than or equal to about 5 % by weight amount exist.In one embodiment, additional optional elements is at least one in cobalt, manganese, zirconium, tantalum, niobium, tungsten, yttrium, titanium, vanadium and hafnium, to form carbide and to improve wear resistance and erosion resistance further.Other optional elements can comprise phosphorus, germanium and arsenic, amounts at the most about 2%, and is preferably less than 1%, to reduce fusing point.In addition, subsidiary impurity should be less than about 2% and be preferably 0.5%.
In certain embodiments, the composition with amorphous alloy can comprise a small amount of impurity.Deliberately can add impurity element to change the attribute of composition, such as improve mechanical property (such as, hardness, intensity, fracture mechanism etc.) and/or improve erosion resistance.Alternatively, impurity can be used as inevitable incidental impurities (such as obtain as processing and the by product that manufactures those) and and to exist.Impurity can be less than or equal to about 10 % by weight, all according to appointment 5 % by weight, all according to appointment 2 % by weight, all according to appointment 1 % by weight, all according to appointment 0.5 % by weight, all according to appointment 0.1 % by weight.In certain embodiments, these per-cents can be volume percent, instead of weight percent.In one embodiment, alloy sample/composition is made up of (only having impurity subsidiary on a small quantity) amorphous alloy substantially.In another embodiment, said composition comprises amorphous alloy (not having observable a little impurity).
In one embodiment, component end item exceedes the critical casting thickness of bulk-solidification type amorphous alloy.
In embodiment herein, wherein bulk-solidification type amorphous alloy can be used as the existence permission superplastic forming of the supercooling liquid phase region that high viscosity liquid exists.Large viscous deformation can be obtained.The ability that large viscous deformation occurs in supercooling liquid phase region is used for be shaped and/or cutting technique.Contrary with solid, liquid block coagulating type alloy local deformaton, this greatly reduces cutting and the energy needed for shaping.Cutting and the easiness be shaped depend on the temperature of alloy, mould and parting tool.Along with temperature is higher, viscosity is lower, therefore cut and be shaped easier.
Embodiment herein can utilize such as with the thermoplastic forming technique that amorphous alloy carries out between Tg and Tx.In this article, according to the standard dsc measurement under typical heating rates's (as 20 DEG C/min), Tx and Tg is defined as the starting point of Tc and the starting point of second-order transition temperature.
Amorphous alloy component can have critical casting thickness, and component end item can have the thickness thicker than critical casting thickness.In addition, select the time of heating and moulding operation and temperature that the elastic strain limit of amorphous alloy can be remained substantially and be not less than 1.0%, and be preferably not less than 1.5%.In the context of embodiment herein, the temperature of about glass transition mean forming temperature can lower than second-order transition temperature, be in second-order transition temperature place or around second-order transition temperature and higher than second-order transition temperature, but to be preferably in lower than Tc T
xtemperature.By the speed similar with the heating rate in heating steps, and preferably carry out cooling step by the speed higher than the heating rate in heating steps.Cooling step also preferably realizes while shaping and moulding loading are still kept.
electronics
Embodiment herein can be valuable in the process using BMG manufacture electronics.Electronics herein can refer to any electronics known in the art.Such as, it can be phone such as mobile telephone and fixed line phone, or any signal equipment such as smart phone (comprises such as iPhone
tM),
And e-mail sending/receiving equipment.It can be indicating meter such as digital indicator, TV monitor, E-book reader, portable web browser (as iPad
tM) and the part of computer monitor.It also can be amusement equipment, comprise Portable DVD player, Conventional DVD players, blue light disc player, video game console, music player such as portable music player (as iPod
tM) etc.It also can be a part for the equipment providing control, such as, control image, video, sound stream (as Apple TV
tM), or it can be the telepilot for electronics.It can be a part for computer or its annex, such as hard disk shell or protective sleeve, laptop computer shell, laptop keyboard, laptop computer Trackpad, desktop computer keyboards, mouse and loud speaker.These goods also can be applicable to the equipment of such as wrist-watch or clock.
The feed comprising BMG can be the raw material in injection moulding.Such as, feed melting also can be injected in mould immediately.The melting feed caused in the speed cooling die of complete unbodied parts can be enough to.Alternatively, the melting feed that can cause the speed of holocrystalline parts (there is the crystalline material more than 99 % by weight) or come with the speed of the parts causing partial crystallization and part amorphous in cooling die.Melting feed is carried out preferably by induction heating.
In embodiment in figure 3, powder is suppressed to form feed.Powder packets is containing the element of BMG, and these elements in powder have the weight percent identical with BMG.Powder can comprise the BMG of powder type.Powder can comprise mixture or the alloy of multiple elements of BMG.Powder can be suppressed together with tackiness agent.Tackiness agent can be at the mixture of the multiple element of one of the material of powder melts temperature gasified, the element of BMG (such as, if BMG comprises Sn, then Sn powder can serve as tackiness agent) or BMG or alloy.In one embodiment, powder is pressed into form feed in jacket, and wherein jacket can not melt under the melt temperature of powder.
In the embodiment illustrated in figure 4, powder to be pressed in jacket to form feed, melts under being wherein wrapped in the melt temperature of powder.Elementary composition on the whole by BMG of powder and jacket, described element has the weight percent identical with BMG.Powder can comprise the BMG of powder type.Powder can comprise mixture or the alloy of multiple elements of BMG.Powder can be suppressed together with tackiness agent.Tackiness agent can be at the mixture of the multiple element of one of the material of powder melts temperature gasified, the element of BMG (such as, if BMG comprises Sn, then Sn powder can serve as tackiness agent) or BMG or alloy.
In one embodiment, the composition of powder can be adjusted to realize the snappiness of the chemical constitution of the parts be made up of feed.Such as, if parts need the Ti of higher per-cent, powder can be regulated by adding the component with more Ti more.Such snappiness allow to manufacture have multiple electrically, magnetic, heat or aesthetic, porosity parts.In one embodiment, can not along with the material of powder smelting during powder can be included in injection moulding, make these parts can be the mixture of the BMG being marked with this material (such as fiber, spheroid).
Can by any appropriate means, such as hot pressing, cold pressing, to extrude or rapid discharge sintering carrys out pressed powder.
BMG feed can be the raw material in injection moulding.Such as, the melting of BMG feed can be injected in mould.The melting BMG in the speed cooling die of complete unbodied parts can be caused.Alternatively, the speed of holocrystalline parts (there is the crystalline material more than 99 % by weight) can have been caused or to cause partial crystallization and the speed of the parts of part amorphous, the melting BMG in cooling die.Melting BMG feed is carried out preferably by induction heating.
Injection moulding is the manufacturing process for preparing parts from thermoplastic and thermoset plastic material.By feed material in the cylindrical shell of heating, mix and push in cavity body of mould, in cavity body of mould, it cools and hardens into the configuration of cavity.Mould, usually by metal, is generally steel or aluminium is made, and carries out precision sizing to form the feature of the parts expected.Injection moulding is widely used in and manufactures from minimum parts to the multiple parts of the whole body panels of automobile.
Polymkeric substance is used in injection moulding.Most of polymkeric substance can be used, be sometimes referred to as resin, comprise all thermoplasticss, some thermosetting materials and some elastomericss.In nineteen ninety-five, have about 18,000 kind of different material can be used for injection moulding, and this numeral is increasing with the mean rate of annual 750 kinds.Available materials is alloy or the mixture of the material of previously exploitation, means that product designer can select just to have the one of correct characteristic from lot of materials is selected.The intensity required based on component end item and function selection material, but often kind of material all has the different parameters that molding must be considered.Common polymkeric substance be the example of thermoset(ting)plastic as epoxy resin and resol, and nylon, polyethylene and polystyrene is thermoplastics.
Injection moulding machine comprises material hopper, injection piston or screw plunger and heating unit.They are also called as press, these are kept at the mould at assembly shaping place.By tonnage to press classification, tonnage represents the amount of the holding force that machine can apply.This power keeps mould to close during injection process.Tonnage from being less than 5 tons to 6000 tons changes, can use higher numeral in relatively few manufacturing operation.By being determined required total holding force by the shadow area of molded parts.For shadow area per square inch, this shadow area is multiplied by the holding force of 2 to 8 tons.As a thumb rule, can be that most of product uses 4 or 5 tons/square inch.If plastic material is stone, it will need larger injection pressure to fill mould, thus need larger clamp tonnage to close to keep mould.Also can determine required power by the material used and part dimension, larger parts need higher holding force.
Mould comprises two primary clusterings, injection mold (A plate) and stripper mould (B plate).Feed enters mould by " cast gate " in injection mold; Sprue bushing wants the nozzle of the injection cylindrical shell of tight seal mould machine, and allows the feed of melting to flow into mould, also referred to as cavity from cylindrical shell.The feed of melting is directed to cavity image by passage by sprue bushing, and passage is processed to the face of A plate and B plate.These passages allow feed to advance along them, therefore referred to as chute.The feed of melting is flowed by chute, and enters one or more special gate, forms the geometrical shape in chamber, to form the parts of expectation.
Can Die and mould plate be drilled through by making refrigerant (normally water) travel across and by the hose connection a series of holes forming continuous path, carry out cooling die.Mould from mould (it absorbs heat from the plastics of heat) heat absorption, and is remained on proper temperature by refrigerant, so as under the most effective speed hardened plastic.
Some moulds allow the parts reinserting previous molding, to allow to form new plastic layer around first component.This is usually called as overmolding.Dichromatism injection moulding or multi-color injection molded mould are designed to carry out " overmolding " within single molding cycle, must process on the special injection molding with two or more injection units.This process is actual is the injection moulding process of execution twice.In a first step, primary colours material is molded as basic configuration, it comprises the space for second time injection moulding.Then by the second material, distinct colors, is injected in those spaces.Such as, can not be worn by the button of this manufacture technics and the marking of button, and still keep high-visible when frequent use.
During parts injection moulding, the sequence of event is called as injection cycle.When mould closes, in the cycle, then feed is injected in cavity body of mould.Once cavity is filled, just maintains and keep pressure to compensate any material contracts.In next step, bolt rotary, is fed to front screw by next injection moulding.This causes screw rod to bounce back when preparing next injection moulding.Once parts fully cool, mould is just opened, and plays injection part.
Claims (amendment according to treaty the 19th article)
1. prepare the method for the feed comprising block metal glass BMG for one kind, described method comprises pressed powder, wherein said powder packets is containing the element of described BMG, and the described element of the described BMG in described powder has the weight percent substantially the same with described BMG, and wherein said powder is suppressed together with tackiness agent.
2. method according to claim 1, wherein said powder comprises the BMG of powder type.
3. method according to claim 1, wherein said powder comprises the mixture of the multiple described element of described BMG.
4. method according to claim 1, wherein said powder comprises the alloy of the multiple described element of described BMG.
5. method according to claim 1, wherein said tackiness agent is the material of the melt temperature gasified at described powder.
6. method according to claim 1, wherein said tackiness agent is one of described element of described BMG, the mixture of multiple described element of described BMG or alloy.
7. method according to claim 1, wherein said powder is pressed in jacket, and wherein said jacket does not melt under the melt temperature of described powder.
8. prepare the method for the feed comprising BMG for one kind, described method comprises powder compression in jacket, wherein said be wrapped in the melt temperature of described powder under melt, wherein said powder comprises described BMG together with described jacket, and the described element of the described BMG in described powder has the weight percent substantially the same with described BMG, and wherein said powder is suppressed together with tackiness agent.
9. method according to claim 8, wherein said powder comprises the BMG of powder type.
10. method according to claim 8, wherein said powder comprises the mixture of the multiple described element of described BMG.
11. methods according to claim 8, wherein said powder comprises the alloy of the multiple described element of described BMG.
12. methods according to claim 1, wherein said tackiness agent is the material of the melt temperature gasified at described powder.
13. methods according to claim 1, wherein said tackiness agent is one of described element of described BMG, the mixture of multiple described element of described BMG or alloy.
14. methods according to claim 1, wherein said powder by hot pressing, cold pressing, extrude or rapid discharge sintering suppress.
15. methods according to claim 8, wherein said powder by hot pressing, cold pressing, extrude or rapid discharge sintering suppress.
16. 1 kinds of utilizations comprise the feed of BMG to prepare the method for parts, described method comprises weight and the composition of determining powder based on the weight of described parts and the composition of expectation, makes the weight of often kind of chemical element in the composition of the described expectation of described parts be substantially equal to the weight of this chemical element of the described BMG in described powder; And suppress described powder to form described feed, wherein said powder is suppressed together with tackiness agent.
17. 1 kinds of utilizations comprise the feed of BMG to prepare the method for parts, described method comprises weight and the composition of determining powder based on the weight of the weight of described parts and the composition of expectation and jacket and composition, makes the weight of often kind of chemical element in the composition of the described expectation of described parts be substantially equal in described powder and the gross weight of this chemical element of described BMG in described jacket; And by described powder compression to described jacket to form described feed, wherein said powder is suppressed together with tackiness agent.
Claims (19)
1. prepare the method for the feed comprising block metal glass (BMG) for one kind, described method comprises pressed powder, wherein said powder packets is containing the element of described BMG, and the described element in described powder has the weight percent substantially the same with described BMG.
2. method according to claim 1, wherein said powder comprises the BMG of powder type.
3. method according to claim 1, wherein said powder comprises the mixture of the multiple described element of described BMG.
4. method according to claim 1, wherein said powder comprises the alloy of the multiple described element of described BMG.
5. method according to claim 1, wherein said powder is suppressed together with tackiness agent.
6. method according to claim 4, wherein said tackiness agent is the material of the melt temperature gasified at described powder.
7. method according to claim 4, wherein said tackiness agent is one of described element of described BMG, the mixture of multiple described element of described BMG or alloy.
8. method according to claim 1, wherein said powder is pressed in jacket, and wherein said jacket does not melt under the melt temperature of described powder.
9. prepare the method for the feed comprising BMG for one kind, described method comprises powder compression in jacket, wherein said be wrapped in the melt temperature of described powder under melt, wherein said powder comprises described BMG together with described jacket, and the described element in described powder has the weight percent substantially the same with described BMG.
10. method according to claim 9, wherein said powder comprises the BMG of powder type.
11. methods according to claim 9, wherein said powder comprises the mixture of the multiple described element of described BMG.
12. methods according to claim 9, wherein said powder comprises the alloy of the multiple described element of described BMG.
13. methods according to claim 9, wherein said powder is suppressed together with tackiness agent.
14. methods according to claim 13, wherein said tackiness agent is the material of the melt temperature gasified at described powder.
15. methods according to claim 13, wherein said tackiness agent is one of described element of described BMG, the mixture of multiple described element of described BMG or alloy.
16. methods according to claim 1, wherein said powder by hot pressing, cold pressing, extrude or rapid discharge sintering suppress.
17. methods according to claim 9, wherein said powder by hot pressing, cold pressing, extrude or rapid discharge sintering suppress.
18. 1 kinds of utilizations comprise the feed of BMG to prepare the method for parts, described method comprises weight and the composition of determining powder based on the weight of described parts and the composition of expectation, makes the weight of often kind of chemical element in the composition of the described expectation of described parts be substantially equal to the weight of this chemical element in described powder; And suppress described powder to form described feed.
19. 1 kinds of utilizations comprise the feed of BMG to prepare the method for parts, described method comprises weight and the composition of determining powder based on the weight of the weight of described parts and the composition of expectation and jacket and composition, makes the weight of often kind of chemical element in the composition of the described expectation of described parts be substantially equal in described powder and the gross weight of this chemical element in described jacket; And by described powder compression to described jacket to form described feed.
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CN1659290A (en) * | 2002-06-13 | 2005-08-24 | 比奇特尔Bwxt爱达荷有限责任公司 | Hard metallic materials, hard metallic coatings, methods of processing metallic materials and methods of producing metallic coatings |
US20060130943A1 (en) * | 2002-07-17 | 2006-06-22 | Atakan Peker | Method of making dense composites of bulk-solidifying amorphous alloys and articles thereof |
CN1737961A (en) * | 2004-08-20 | 2006-02-22 | 阿尔卑斯电气株式会社 | Coil-embedded dust core |
JP2011235344A (en) * | 2010-05-13 | 2011-11-24 | Porite Corp | Method for manufacturing glassy metal product, and dissimilar material composite |
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US20150307967A1 (en) | 2015-10-29 |
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CN104583435B (en) | 2019-05-17 |
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