CN103946406A - Alloying technique for fe-based bulk amorphous alloy - Google Patents

Abstract

One embodiment provides a method of making an alloy feedstock, comprising: forming a first composition by combining Fe with a first nonmetal element; forming a second composition by combining Fe with a plurality of transition metal elements; forming a third composition by combining the second composition with a second nonmetal element; and combining the first composition with the third composition to form an alloy feedstock.

Description

For the alloying process of iron-base block amorphous alloy

All publications, patent and the patent application quoted in this manual is all incorporated to way of reference accordingly in full.

Background technology

The current most of metal alloy using is at least at first by solidifying casting processing.Metal alloy melts and waters and casts from metal or ceramic die, solidifies therein.Peel off mould, the metalwork of casting can use or further processing.The as-cast structure that solidifies the most of materials that produce with cooling period depends on rate of cooling.The character changing does not have general rule, but for most of parts, structural changes is only accompanied by the variation of rate of cooling gradually.On the other hand, for bulk-solidification type amorphous alloy, the variation between the metamict of relatively quick cooling generation and the crystalline state of relatively slow cooling generation be matter variation but not amount variation (two states have different characteristics).

Bulk-solidification type amorphous alloy or block metal glass (" BMG ") are a metalloid material of developing recently.These alloys can solidify with cooling with relatively slow speed, and they at room temperature keep unbodied noncrystalline (, vitreous state) state.This metamict can be very advantageously for some application.The manufacture of amorphous alloy can relate to alloy raw material is molten into molten state, makes subsequently fused raw material quench and generates final alloy form.The method of current raw materials is usually directed to powdered alloy to be pressed into ingot bar.But the size of raw material ingot bar is conventionally very little, because powder compression does not produce large size product.In addition, raw material is inhomogeneous with respect to chemical composition conventionally, because different chemical constitutions does not have the possibility of homogeneous distribution.A result of local inhomogeneity is to lack amorphous phase, because amorphous alloy is to its chemical constitution sensitivity conventionally.In addition, this type of restriction can be the challenge of manufacturing as the amorphous alloy of construction package, because compared with powder compact, parts need the relatively large ingot bar of size conventionally.

Therefore, exist exploitation can manufacture the needs of the method that can be used for the raw material of manufacturing bulk amorphous alloys, described raw material be homogeneous and also size quite large.

Summary of the invention

An embodiment provides the method for preparing alloy raw material, and it comprises: by iron and the first non-metallic element are combined to form to the first composition; By iron and multiple transition metal are combined to form to the second composition; By the second composition and the second non-metallic element are combined to form to the 3rd composition; And by the first composition and the 3rd combination of compositions to form alloy raw material.

Alternative embodiment provides the method for preparing alloy raw material, and it comprises: by iron and the first non-metallic element are combined to form to the first composition; By iron and multiple transition metal and carbon are combined to form to carbonaceous composition; The first composition and carbonaceous composition are combined to form alloy raw material.

Another embodiment provides the method for preparing alloy raw material, and it comprises: provide iron content the first composition; By carbon with the second combination of compositions of comprising molybdenum, chromium and yttrium to form the 3rd composition; And by the first composition and the 3rd combination of compositions to form alloy raw material.

Brief description of the drawings

Fig. 1 provides the schematic diagram of the prealloy composition forming during the intermediate steps of method in an embodiment.Said composition has some that be found to provide unexpected results needed and stacks order.

Fig. 2 provides the alternative view that stacks order of the prealloy composition of describing in Fig. 1.

Fig. 3 provides the schematic diagram that forms another prealloy in an embodiment, and wherein another prealloy composition is arranged at the top of carbon granule, to allow forming different carbon containing prealloy compositions from prealloy and carbon.

Fig. 4 shows in an embodiment for the different elements of alloying process and the picture of relative dimension (compared with scale) (non-powder part all has at least one for about 5mm or larger size) thereof.

Fig. 5 shows the picture of Fe-Mo-Cr mother alloy in an embodiment (or prealloy composition) ingot bar.

Fig. 6 (a)-6 (b) shows the alloy ingot obtaining in contrast test in an embodiment, wherein separates all crushing members and collects flue dust.

Fig. 7 shows the alloy ingot picture obtaining during contrast test in an embodiment, and wherein ingot bar is fragility, and when cooling, is broken into multiple smallclothes.

Fig. 8 (a)-8 (c) show the alloy raw material made according to embodiments of the invention and by raw material by extra melting again and the amorphous alloy of making of casting.

Fig. 9 (a)-(b) show two respectively from the DSC thermography curve of 6mm and the collection of 8mm casting rod, described casting rod is produced by the raw material obtaining from embodiments described herein.

Embodiment

phase

Term " phase " herein can refer to the phase of finding in thermodynamics phasor.Substantially be region, consistent space (as, thermodynamical system) for spreading all over all physical propertys of material wherein mutually.The example of physical property comprises density, specific refractory power, chemical constitution and lattice period.By be described as simply mutually material chemically unanimously, different physically and/or region that can mechanical separation.For example, in the system being made up of ice and water in glass pot, ice cube is a phase, and water is second-phase, and side's waterborne wet air is third phase.The glass of tank is the another kind of phase that separates.Can refer to mutually sosoloid, it can be binary, ternary, quaternary or more polynary solution or compound, for example intermetallics.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 being found in the periodic table of elements.Physically, the atoms metal in ground state comprises the band being partially filled, and has the empty state of the occupied state of approaching.Term " transition metal " is any metallic element in the 3rd 12 families of family to the in the periodic table of elements, and it has incomplete inner shell, and in series of elements, between maximum positive polarity and minimum positive polarity, plays the effect that transition connects.Transition metal is characterised in that multiple valency, coloured compound and forms the ability of stable complexing ion.

Term " nonmetal " refers to not have the chemical element of losing electronics and forming cation capacity.Depend on application, can use any suitable non-metallic element or their combination.Alloy composite can comprise multiple non-metallic element, for example at least two kinds, at least three kinds, at least four kinds or more kinds of non-metallic element.Non-metallic element can be any element seeing in the 13-17 family of the periodic table of elements.For example, non-metallic element can be any 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 can be also some metalloid in 13-17 family.

In certain embodiments, metalloid is in the periodic table of elements, to distinguish the element that metal and nonmetallic stepped line find.This line is plotted to the border between polonium and astatine between boron and aluminium.Metalloid has metal and nonmetal the two characteristic.Some metalloids (for example silicon and germanium) are semi-conductors, and for example they can be with electric charge under special conditions.Some common known metalloids can comprise at least one metalloid of for example B, Si, Ge, As, Sb, Te and Po.In one embodiment, non-metallic element can comprise B, Si, C, P or their combination.Therefore, for example, alloy composite can comprise boride, carbide or the two.

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, Lu Jin (rutherfordium), Jin shut out (dubnium), Jin likes (seaborgium), beryllium, Jin black (hassium), Jin wheat (meitnerium), Jin reaches (ununnilium), any in Jin logical sequence (unununium) and ununbium.In one embodiment, the BMG that comprises 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, can use any suitable transition metal or their combination.Described alloy composite can comprise multiple transition metal, for example at least two kinds, at least three kinds, at least four kinds or more kinds of transition metal.

Alloy described in the invention or alloy " sample " or " sample " alloy can have any shape or size.For example, described alloy can have particulate form, and it for example can have spherical, ellipsoid shape, wire, shaft-like, sheet, laminar or erose shape.Particulate can have any suitable size.For example, it can have the mean diameter between approximately 1 micron and approximately 100 microns, for example, between between approximately 5 microns and approximately 80 microns, for example, between between approximately 10 microns and approximately 60 microns, for example, between between approximately 15 microns and approximately 50 microns, for example, between between approximately 15 microns and approximately 45 microns, for example, for example, between between approximately 20 microns and approximately 40 microns, between approximately 25 microns and approximately 35 microns.For example, in one embodiment, the mean diameter of particulate is between approximately 25 microns and approximately 44 microns.In certain embodiments, can use for example particulate in nanometer range of less particulate, or larger particulate is for example greater than 100 microns those.

Alloy sample or sample can also have much bigger yardstick.For example, it can be block structure assembly, for example shell/protective sleeve of ingot bar, electronics or or even have millimeter, centimetre or meter within the scope of the part of construction package of yardstick.

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 to be bonded to each other and the composition of two or more materials that conventionally can separate.In general, these two or more materials Chemical bond not each other not.

alloy

In certain embodiments, alloy composite as herein described can be by complete alloying.In one embodiment, " 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 other metals; For example, brass is the alloy of zinc and copper.Different from mixture or intermetallics, alloy can refer to one or more elements in metallic matrix sosoloid partially or completely.Term " alloy " herein can refer to the part solution that can provide the complete solid solution alloy of single solid phase microstructure and can provide two or more phases both.

Therefore, completely the alloy of alloying can have the composition of homogeneous distribution, no matter be solid solution phase, Compound Phase or the two.Term as used herein " alloying completely " can be considered the subtle change in error margin.For example, it can refer at least 90% alloying, for example at least 95% alloying, for example at least 99% alloying, for example at least 99.5% alloying, for example 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 by impurity balance, and it,, with regard to composition or mutually, may not be a part for alloy.

amorphous or non-crystalline solids

" amorphous " or " non-crystalline solids " is the solid lacking as the lattice period of crystal property.As used herein, " amorphous solid " comprises " glass ", and it is the amorphous solid that is softened and be transformed into class I liquid I state in the time of heating by glass transition phase.In general, although amorphous material can have some short range orders because of the character of chemical bond under atomic length yardstick, their lack the long-range order characteristic of crystal.Based on passing through structural characterization technology such as X-ray diffraction and the determined lattice period of transmission electron microscopy, can distinguish amorphous solid and crystalline state solid

Term " in order " and " unordered " are specified the existence of some symmetry in many-particle system or dependency or are not existed.Term " long-range order " and " short range order " based on length dimension distinguish in material in order.

In solid the strictest form be lattice period in order: constantly repeat certain pattern (atomic arrangement in structure cell) to form translation invariant space splicing (tiling).This is the definition character of crystal.Possible symmetry is divided into 14 Bradley dimension (Bravais) lattices and 230 spacers.

Lattice period sexual cue long-range order.If an only known structure cell, can predict all atom sites in any distance exactly by translational symmetry.Normally correct conversely, except for example thering is the splicing of perfect determinacy but not having in the quasicrystal of lattice period.

Long-range order characterizes the physical system that the remote part of same sample wherein represents related behavior.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 particular system.In the time of x=x', this function equals 1, and along with distance | x-x'| increases and reduces.Conventionally, it is in larger distance exponential attenuation to zero, and thinks that this system is unordered.But, if relevance function is large | x-x'| place decays to constant value, can think that this system has long-range order.If its power as distance decays to zero, can be called accurate long-range order.Note, the numerical value of so-called " large | x-x'| " is relative.

In the time that some parameters of its behavior of definition are time-independent stochastic variable, they are quenchings or freezing, can think that system presents quenching unordered, and if spin glass is in the time allowing stochastic variable Self-variation, it is unordered contrary with annealing.Embodiment herein comprises and comprises the unordered system of quenching.

Alloy as herein described can be crystalline state, part crystalline state, unbodied or substantially unbodied.For example, alloy sample/sample can comprise at least some degree of crystallinity, has the crystal grain/crystal of the size in nanometer and/or micrometer range.Alternatively, alloy can be substantially unbodied, for example completely unbodied.

In one embodiment, the existence in extra other amorphous alloy of crystal or multiple crystal can be regarded as " crystallization phases " wherein.The degree of crystallinity degree (or in certain embodiments referred to as " degree of crystallinity ") of alloy can refer to be present in the amount of the crystallization phases in alloy.Described degree can refer to for example be present in the mark of the crystal in alloy.Described mark can refer to volume fraction or weight fraction, and this depends on context.Measuring of " amorphous " to amorphous alloy can be amorphous degree.The degree of the available degree of crystallinity of amorphous degree is weighed.For example, in one embodiment, the alloy with the degree of crystallinity of low degree can be considered to have the amorphous degree of high level.In one embodiment, for example, the alloy with 60 volume % crystallization phasess can have 40 volume % amorphous phases.

amorphous alloy or amorphous metal

" amorphous alloy " be greater than for having 50 volume % amorphous content, be preferably greater than the amorphous content of 90 volume %, more preferably greater than the amorphous content of 95 volume % and be most preferably greater than 99 volume % to the alloy of the amorphous content of 100 volume % almost.Note, as mentioned above, it is low that the alloy that amorphous degree is high is equivalent to degree of crystallinity degree." amorphous metal " is for having the amorphous metallic material of unordered atomicscale structure.Compared with being the most metals of crystallization the atomic arrangement therefore with high-sequential, amorphous alloy is amorphous.The material that wherein this disordered structure is directly produced by the liquid state of cooling period is called as " glass " sometimes.Therefore, conventionally amorphous metal is called to " metallic glass " or " glassy metal ".In one embodiment, " block metal glass " (" BMG ") can refer to that its microstructure is unbodied alloy at least in part.But, except extremely fast cooling, also exist several method to produce amorphous metal, comprise physical vapor deposition, solid state reaction, ion irradiation, solution spinning and mechanical alloying.No matter how amorphous alloy is prepared, they may be unitary class material.

Amorphous metal can produce by multiple method for rapid cooling.For example, can be by molten metal be splashed on rotating metallic dish and produces amorphous metal.About degree up to a million per second quick cooling may be too fast for crystal formation, and therefore by material " locking " in vitreousness.In addition, can be with so low that to be enough to allow amorphous structure formation critical cooling rate in thick-layer to produce amorphous metal/alloy, as block metal glass.

Term " block metal glass " (" BMG "), bulk amorphous alloys and bulk-solidification type amorphous alloy use in this article interchangeably.They refer to have at least amorphous alloy of the smallest dimension within the scope of millimeter.For example, described yardstick can be at least about 0.5mm, for example at least about 1mm, for example at least about 2mm, for example at least about 4mm, for example at least about 5mm, for example at least about 6mm, for example at least about 8mm, for example at least about 10mm, for example, at least about 12mm.Depend on geometrical shape, described yardstick can refer to diameter, radius, thickness, width, length etc.BMG also can be and have in cm range (for example at least about 1.0cm, for example at least about 2.0cm, for example at least about 5.0cm, for example, at least about 10.0cm) the metallic glass of at least one yardstick.In certain embodiments, BMG can have at least yardstick of at least one within the scope of rice.BMG can present above-mentioned any shape or the form relevant with metallic glass.Therefore, in certain embodiments, BMG as herein described may be different from an importance film of making by conventional deposition technique---and the former can have the yardstick more much bigger than the latter.

Amorphous metal can be alloy, instead of pure metal.This alloy can comprise the atom of remarkable different size, thereby causes the low free volume (and therefore having than the viscosity of other metals and the higher order of magnitude of alloy) in melted state.This viscosity prevents that atom is fully mobile to form orderly lattice.Material structure can cause the low-shrinkage of cooling period and the resistivity to viscous deformation.The crystal boundary weakness of crystalline material (in some cases for) not there is not the better resistivity that can for example cause abrasion and corrosion.In one embodiment, also comparable oxide glass and ceramic much tough and tensile and so not crisp of amorphous metal (technical saying, that is glass).

The thermal conductivity of amorphous material can be lower than the thermal conductivity of its crystalline state counterpart.Even in order still to realize the formation of amorphous structure during compared with Slow cooling, this alloy can be made up of three kinds or more kinds of component, thereby causes having the complex crystals unit compared with high potential energy and lower formation probability.The formation of amorphous alloy can be depending on multiple factors: the composition of the component of alloy; The atomic radius of component (preferably have and exceed 12% remarkable difference to obtain high-bulk-density and low free volume); And the combination of blending ingredients, suppress crystal nucleation and extend the negative heat of the time of molten metal in overcooling state.But, because the formation of amorphous alloy is based on a lot of different variablees, therefore may be difficult to determine in advance whether alloy composite can form amorphous alloy.

For example, the amorphous alloy with boron, silicon, phosphorus and other glass forming agents of magneticmetal (iron, cobalt, nickel) can be magnetic, has low Coercive Force and high resistance.High resistance causes in the time standing alternating magnetic field because of the low-loss due to eddy current, for example, as the useful quality of magnetic core of transformer.

Amorphous alloy can have the character 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 (for example dislocation) of restriction crystal alloy intensity.For example, a kind of modern amorphous metal, is called Vitreloy ^tM, there is the tensile strength of the twice of the tensile strength that is almost senior titanium.In certain embodiments, the metallic glass under room temperature is not ductile and in the time loading, tends to sudden failure under stressing conditions, and this has limited the material applicability in reliability-critical applications, because imminent inefficacy is sightless.Therefore, in order to overcome this challenge, can use the metal matrix composite materials of the metallic glass matrix with the dendrite particle that comprises ductile crystalline state metal or fiber.Alternatively, can use one or more elements (for example, the Ni) BMG that content is low that tends to cause embrittlement.For example, can improve with the BMG that does not contain Ni the ductility of BMG.

Another useful quality of bulk amorphous alloys is that they can be genuine glass; In other words, they can be softening and mobile in the time of heating.Can allow simply to process with the almost identical mode of polymkeric substance, for example, by injection moulding.Therefore, can prepare sports equipment, medical facilities, electronic package and equipment and film with amorphous alloy.Can be via the film of high-velocity oxy-fuel deposition techniques amorphous metal as protective coating.

Material can have amorphous phase, crystallization phases or both.Amorphous phase and crystallization phases can have identical chemical constitution and only different in microstructure, and one is amorphous microstructure and another one is crystalline microstructure.Microstructure in one embodiment refers to by microscope with 25 x magnifications or the structure of material that more high power shows.Alternatively, these two phases can have different chemical constitutions and microstructure.For example, composition can be amorphous, the essentially no setting of part or completely unbodied.

As mentioned above, can measure by the crystalline fraction existing in alloy the degree (otherwise and being the degree of degree of crystallinity) of amorphous degree.This degree can refer to volume fraction or the weight fraction of the crystallization phases existing in alloy.Part amorphous compositions can refer to its at least about 5 volume % (for example at least about 10 volume %, for example at least about 20 volume %, for example at least about 40 volume %, for example at least about 60 volume %, for example at least about 80 volume %, for example, at least about 90 volume %) be the composition of amorphous phase.Term " substantially " and " approximately " are defined at the application's elsewhere.Therefore, at least substantially unbodied composition can refer to its at least about 90 volume % (for example at least about 95 volume %, for example at least about 98 volume %, for example at least about 99 volume %, for example at least about 99.5 volume %, for example at least about 99.8 volume %, for example, at least about 99.9 volume %) for unbodied composition.In one embodiment, unbodied composition can have in the crystallization phases of some subsidiary slight amounts that wherein exist substantially.

In one embodiment, with respect to amorphous phase, amorphous alloy composition can be homogeneous.On composition, the material of homogeneous is homogeneous.This be that heterogeneous material is contrary.Term " composition " refers to chemical constitution and/or the microstructure in material.In the time the volume of material being divided into two halves and two halves and all having substantially the same composition, this material is homogeneous.For example, in the time that the volume dimidiation of microparticle suspending liquid and two halves all have the particle of substantially the same volume, this microparticle suspending liquid is homogeneous.But, may see under the microscope independent particle.Another example of homogeneous substance is air, although airborne particle, gas and liquid can be analyzed separately or separate from air, heterogeneity wherein equally suspends.

The composition that is homogeneous with respect to amorphous alloy can refer to have in its whole microstructure the composition of equally distributed amorphous phase substantially.In other words, in said composition macroscopic view, be included in whole composition equally distributed amorphous alloy substantially.In an alternative embodiment, said composition can be the mixture with amorphous phase, have non-amorphous phase, or vice versa in this amorphous phase.This non-amorphous phase can be a kind of crystal or multiple crystal.Crystal can be any shape for example spherical, elliposoidal, linear, rod, sheet shape, slice-shaped or erose particulate form.In one embodiment, it can have dendrite form.For example, at least part of unbodied composite composition can have the crystallization phases of the dendrite shape being scattered in amorphous phase matrix; 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, crystallization phases can more easily extend mutually than BMG.

Method as herein described can be applicable to the amorphous alloy of any type.Similarly, the amorphous alloy of describing as the composition of composition or goods herein 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., this alloy can comprise any combination of these elements with its chemical formula or chemical constitution.Described element can exist with different weight or meausurement per-cent.For example, iron " base " alloy can refer to that the iron with non-slight weight percent is present in alloy wherein, this weight percent for example can be at least about 40 % by weight, for example at least about 50 % by weight, for example at least about 60 % by weight, for example, at least about 80 % by weight.Alternatively, in one embodiment, per-cent mentioned above 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.In certain embodiments, this alloy or comprise that the composition of alloy can not basically contain nickel, aluminium or beryllium or their combination.In one embodiment, completely not nickeliferous, the aluminium of this alloy or mixture or beryllium or their combination.

For example, amorphous alloy can have formula (Zr, Ti) _a(Ni, Cu, Fe) _b(Be, A1, Si, B) _c, wherein a, b and c represent weight or atomic percent separately.In one embodiment, in atomic percent, a is in 30 to 75 scope, and b is in 5 to 60 scope, and c is in 0 to 50 scope.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, in atomic percent, a is in 40 to 75 scope, and b is in 5 to 50 scope, and c is in 5 to 50 scope.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, in atomic percent, a is in 45 to 65 scope, and b is in 7.5 to 35 scope, and c is in 10 to 37.5 scope.Alternatively, alloy can have formula (Zr) _a(Nb, Ti) _b(Ni, Cu) _c(A1) _d, wherein a, b, c and d represent weight or atomic percent separately.In one embodiment, in atomic percent, a is in 45 to 65 scope, and b is in 0 to 10 scope, and c is in 20 to 40 scope, and d is in 7.5 to 15 scope.An exemplary embodiment of aforementioned alloy system is by Liquidmetal Technologies, CA, the commodity Vitreloy by name that USA manufactures ^tMthe Zr-Ti-Ni-Cu-Be base amorphous alloy of (for example Vitreloy-1 and Vitreloy-101).Some examples of the amorphous alloy of different system are provided in table 1.

Amorphous alloy also can be iron alloy, for example (Fe, Ni, Co) base alloy.The example of such composition is in U.S. Patent No. 6,325, and 868,5,288,344,5,368,659,5,618,359 and 5,735,975, the people such as Inoue, Appl.Phys.Lett. the people's such as (the 71st the 464th page of volume (1997)), Shen Mater.Trans., has disclosed in JIM (the 42nd the 2136th page of volume (calendar year 2001)) and Japanese patent application No.200126277 (publication number 2001303218A).A kind of exemplary composition is Fe ₇₂al ₅ga ₂p _llc ₆b ₄.Another example is Fe ₇₂al ₇zr _l0mo ₅w ₂b ₁₅.The another kind of ferrous alloy system can be used in this paper coating is disclosed in U.S. Patent Application Publication No.2010/0084052, wherein amorphous metal comprises for example 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, and the compositing range of appointment provides in bracket.

Aforesaid amorphous alloy system also can comprise extra element, and for example extra transition metal, comprises Nb, Cr, V and Co.The amount that described extra element can be being less than or equal to approximately 30 % by weight, be for example less than or equal to approximately 20 % by weight, be for example less than or equal to approximately 10 % by weight, be for example less than or equal to approximately 5 % by weight exists.In one embodiment, extra optional elements is at least one in cobalt, manganese, zirconium, tantalum, niobium, tungsten, yttrium, titanium, vanadium and hafnium, to form carbide and further to improve wear resistance and erosion resistance.Other optional elements can comprise phosphorus, germanium and arsenic, total amount at the most approximately 2%, and be preferably less than 1%, to reduce fusing point.Subsidiary impurity in addition should be less than approximately 2% and preferably 0.5%.

In certain embodiments, the composition that has an amorphous alloy can comprise a small amount of impurity.Can specially add impurity element to change the character of composition, for example improve mechanical properties (as, hardness, intensity, fracture mechanism etc.) and/or improve erosion resistance.Alternatively, impurity can be used as inevitable incidental impurities (those as obtained as the by product of processing and manufacture) and exists.Impurity can be less than or equal to approximately 10 % by weight, for example approximately 5 % by weight, for example approximately 2 % by weight, for example approximately 1 % by weight, for example approximately 0.5 % by weight, for example approximately 0.1 % by weight.In certain embodiments, these per-cents can be volume percent, instead of weight percent.In one embodiment, alloy sample/composition forms (only having a small amount of incidental impurities) by amorphous alloy substantially.In another embodiment, said composition comprises amorphous alloy (there is no observable trace impurity).

Table 1: exemplary amorphous alloy moiety

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

Sn

?

?

50.75％

36.23％

4.03％

9.00％

0.50％

?

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

Au

Ag

Pd

Cu

Si

?

?

49.00％

5.50％

2.30％

26.90％

16.30％

?

13

Au

Ag

Pd

Cu

Si

?

?

50.90％

3.00％

2.30％

27.80％

16.00％

?

14

Pt

Cu

Ni

P

?

?

?

57.50％

14.70％

5.30％

22.50％

?

?

15

Zr

Ti

Nb

Cu

Be

?

?

36.60％

31.40％

7.00％

5.90％

19.10％

?

16

Zr

Ti

Nb

Cu

Be

?

?

38.30％

32.90％

7.30％

6.20％

15.30％

?

17

Zr

Ti

Nb

Cu

Be

?

?

39.60％

33.90％

7.60％

6.40％

12.50％

?

18

Cu

Ti

Zr

Ni

?

?

?

47.00％

34.00％

11.00％

8.00％

?

?

19

Zr

Co

Al

?

?

?

?

55.00％

25.00％

20.00％

?

?

?

alloy raw material is manufactured

The method that the present invention describes can relate to preparation can be subsequently for the manufacture of the alloy raw material of BMG.BMG can be any aforementioned alloy composite.In one embodiment, BMG is iron alloy, for example ferrous alloy.In one embodiment, alloy can have chemical formula Fe ₄₈cr ₁₅mo ₁₄c ₁₅b ₆y ₂.Note, multiple other ferrous alloys are also feasible.Alloy raw material can have the chemical constitution identical with final BMG, although do not need so.In one embodiment, alloy raw material has the chemical constitution identical with the BMG manufacturing subsequently, but has different degree of crystallinity.For example, in one embodiment, alloy raw material can be not exclusively unbodied, and for example crystallization substantially, as complete holocrystalline.

In one embodiment, the method for preparing alloy raw material can comprise at least two steps, and each step relates to prepares prealloy composition.Can be identical or different from the prealloy composition of different step.Although the final product (, alloy raw material) that the method for describing according to the present invention in some embodiment produces can be the alloy of homogeneous, " the prealloy composition " of indication needs not to be alloy or homogeneous herein.For example, in one embodiment, any prealloy composition can be compound, for example intermetallics.Or composition can be mixture.In addition, in certain embodiments, prealloy composition and/or alloy raw material are homogeneous with respect to chemical constitution.But prealloy composition, or alloy raw material even, need not to be complete homogeneous, especially with respect to chemical constitution.For example, they can be homogeneous in its some part, but in other parts are not.Or they can not be homogeneous.

In one embodiment, provide the method for preparing alloy raw material, the method can comprise some intermediate steps.For example, the method can relate to a series of prealloys that can combine subsequently of formation.The method can relate to ferro element and the first non-metallic element are combined to form to the first composition; Iron and multiple transition metal are combined to form to the second composition; The second composition and the second non-metallic element are combined to form to the 3rd composition; And make the first composition and the 3rd composition alloying form alloy raw material.In one embodiment, alloy raw material comprises iron alloy, and for example iron containing alloy, as ferrous alloy.Element can be any size or shape.Compared with the method that depends on powder compression being pre-existing in, at least some elements used in embodiments described herein have at least one size, this size is far longer than generally " powder " size, as grade or larger, for example at least about 1mm, for example at least about 2mm, for example at least about 2mm, for example, at least about 5mm.In one embodiment, all elements has at least one grade or larger size.In another embodiment, this size refers to minimum size.

In one embodiment, the first prealloy composition can be compositions including iron, for example compound, for example intermetallics in one embodiment.For example, or the first prealloy composition can be alloy, iron containing alloy.Non-metallic element can be any aforementioned metalloid.For example, it can be B, P, Si, Ge, C or their combination.Therefore, the first composition can comprise FeB, iron phosphide etc.For example, the first composition can comprise Fe ₂b, FeB, FeSi, FeSi ₂, Fe ₃p or their combination.In certain embodiments, these compounds can obtain by coarse powder conventionally, for example commercially available powder.Or they can be large size " pieces ", as above-mentioned grade.In one embodiment, Elements C (and other elements) can be by adding with alloy or mixing, for example white pig iron or graphitic pig iron, and it conventionally can have and comprises Fe, C, Si and the composition of other elements on a small quantity.In some alternative embodiment, manual pre-alloyed step as herein described can be used for combining various elements, compound and/or alloy and forms mother alloy/prealloy with original position, and does not use the compound and the alloy that are pre-existing in.Example can be Fe-Cr-Mo ingot bar or the Fe-B mother alloy ingot bar as herein described that this paper and non-limiting working example part are described.Referring to Fig. 5.

The second prealloy composition can comprise multiple transition metal.Transition metal can be any combination of aforementioned transition metal.In one embodiment, element can comprise at least one in Fe, Mo, Cr, Ni, Y, Co, Mn, Ga and Er.In one embodiment, the second composition can comprise Fe, Mo, Cr, Y, Co, Mn, Ga and Er.In another embodiment, composition can be made up of Fe, Mo, Cr, Y, Co, Mn, Ga and Er substantially.In one embodiment, the second composition can be made up of Fe, Mo, Cr, Y, Co, Mn, Ga and Er.

The second non-metallic element can be also any nonmetal, comprises above-mentioned metalloid.For example, it can be C, can be maybe as the first metalloid B or P.Carbon can graphite form, or any other suitable carbon source supply.Transition metal can stack with some order during this fusing/alloying.In certain embodiments, it can be unusual important stacking order.Specifically, in certain embodiments, if can produce any raw material completely, can produce the alloy raw material with inferior character from different stacking sequentially described herein.For example, in one embodiment, with respect to the composition without the order of stacking, described formation can have at least one the lower evaporation in Fe and Cr unexpectedly for the second prealloy composition.The evaporation of element can be less desirable in certain embodiments, because therefore the loss of element can increase recovery time and/or cost.

In one embodiment, stacking order can be that Mo is arranged on Fe above, and it is upper that Fe is arranged on Cr, and it is upper that Cr is arranged on Y, as shown in Figure 1.Note, order is herein only schematically, and if for example composition inversion, can put upside down.Stacking order also can be perpendicular to shown in Fig. 1.For example, it can be from left to right, or turn left from the right side.In one embodiment, the high melting temperature that Mo can have in all four kinds of elements.Fig. 5 shows the image of Fe-Mo-Cr mother alloy (or prealloy) ingot bar in an embodiment.Ingot bar can be with respect to component homogeneous, but needs in all embodiments and not all so.Be not subject to the constraint of any particular theory, Mo can be used as the interim barrier of other elements, to reduce the possibility of thermal shocking.During this alloying/combination step, individual element is fusible and with the fusion of any particular order and another kind of element.For example, in this embodiment, first Fe can fuse with Mo, and then Cr can fuse with middle Fe-Mo composition; Last Y can fuse with Fe-Mo-Cr composition.Therefore,, in the time of Y and this second prealloy composition of other elements fusion formation, prealloy composition can be with respect to these element homogeneous.Or in another embodiment, second prealloy needs not to be homogeneous.

In one embodiment, because the combination of element has increased temperature and mixing, its can blend for thering is capillary homogeneous liquid to a certain degree.Surface tension can be tending towards that melting is dripped and pull into the ingot bar (or " button ingot casting ") of sub-circular, and gravity is tending towards its pressing.Depend on the size of ingot bar, because it is homogeneous, therefore its formation has the dish type at cavetto edge, and can during arc-melting process, clearly observe the transformation that the circle from different heat block to homogeneous alloy drips.In some cases, this transformation is called " cavetto ".

In one embodiment, in the beginning that forms the 3rd composition, the second non-metallic element can be arranged under the second composition.In one embodiment, the 3rd prealloy composition can form by the second non-metallic element and the second combination of compositions.For example, if the second non-metallic element is carbon, the 3rd composition can be carbonaceous composition.Combination can be carried out by any structure.For example, carbon can be the form of multiple particulates (for example graphite granule).Particle can be placed under the second prealloy composition before fusing/alloying step.Or carbon can be placed in top or the side of the second prealloy composition.In one embodiment, the composition that the 3rd prealloy composition can comprise Fe-Mo-Cr-Y-C alloy or comprise these elements.Note, in alloy as herein described, the order of the symbol of element can change and not change the implication of alloy.

Fusing as herein described and alloying can be undertaken by any suitable heating technique.For example, heating can relate to arc-melting, vacuum induction melting (VIM), photoflash lamp, resistance furnace, laser, electron beam or their combination.After each fusing/combination step (and during), prealloy composition can be cooled to lesser temps, for example room temperature.Depend on composition used and smelting technology, (time) vary in length of the each combination step in method as herein described.In one embodiment, at least some combination step can be carried out approximately at least 10 minutes, for example at least about 20 minutes, for example, at least about 30 minutes.Therefore, in one embodiment, the whole preparation process of alloy raw material can be carried out approximately at least 1 hour, for example, for example, at least about 1.5 hours, at least 2 hours.The combination that forms the term of step for any prealloy herein can refer to the combination of any type, comprises physical combination and/or chemical association.For example, combination can refer to alloying and/or mix multiple element, for example, between melting period.Or, depend on linguistic context, combination can refer to that chemistry forms new compound.

Wherein heat in the embodiment being undertaken by arc-melting at one, between melting period alloy electric charge or prealloy composition mixture fusible and/or upset.In one embodiment, " fusing " in arc-melting can refer to use arc-melting (metal) element and make the process that they fuse/mix.Electric arc can have and infiltrates molten metal mixture and make the ability that they mix.In certain embodiments, if electric arc is mobile with some figure (or multiple figure), can realize height homogeneity.But, conventionally can there are some unfused metal blocies, its be deposited in melt bottom (at cooling center) and keep not fusing (as, in its pure/primitive form).In some cases, can stop electric arc, make the cooling formation solid of mixture, then mixture (or button ingot casting or ingot bar) can overturn always, the egg of decocting as overturn pancake or two sides.After upset, electric arc can reopen, and button ingot casting can start from the fusing of button ingot casting edge and slowly stride across button ingot casting to move.As time goes on, can find unfused, and electric arc can concentrate on these pieces, make them be molten into mixture.

In certain embodiments, " upset " also can refer to tumble mixed thing, to promote before to homogenize in above-mentioned each " fusing ".For example, " melt for 4 times and 3 upsets " and can refer to following order in one embodiment: fusing, wait is solidified, upset, fusing, wait is solidified, overturns, fusing, wait is solidified, upset and fusing.In this embodiment, the unfused metal/alloy piece of high-density can sink to bottom, and unfused of low density can keep floating.In one embodiment, can overturn, because metal melts on the water-cooled part of copper.The bottom of ingot bar can approach the temperature of copper, and electric-arc heating is directly passed through at top.Therefore, this means the most intensive element and not exclusively mixed before it sinks to bottom conventionally, and when they sink to when bottom, they in ingot bar compared with cool region, therefore they stop dissolving.Therefore, in certain embodiments, make the cooling and manual overturning of whole ingot bar.Once electric arc reopens, can heat was once the bottom of ingot bar, and inhomogeneity is dissolved more before sinking to.Therefore, can reduce the not fusing part that embeds ingot bar, and ingot bar can become more homogeneous along with each upset and refuse subsequently.

The raw material that the method for embodiment more provided herein produces can be the form of button ingot casting or ingot bar, and these two terms are used interchangeably in embodiment more as herein described.Raw material button ingot casting or ingot bar can have any shape or size.For example, ingot bar can be cylindrical, spherical, cube or have during any shape or irregularly shaped.Raw material also can be taked any size or the shape of aforementioned alloy sample.As mentioned above, raw material can be homogeneous, is especially homogeneous with respect to chemical constitution.In certain embodiments, whole raw material can be homogeneous.In some alternative embodiment, raw material only therein some region can be homogeneous, raw material only has local uniformity, without block uniformity.Having high uniformity is that unusual important BMG alloy especially as herein described can be very responsive to chemical constitution, and inhomogeneity can cause the chemical constitution of the change of different positions in raw material.Therefore, as described below, inhomogeneity can cause the existence of non-amorphous phase.

Raw material can have millimeter scope or larger, for example cm range or larger size, and this large size can be different from the raw material of the powder compression generation of the different elements of the powder type being pre-existing in.In one embodiment, raw material can have at least one and be at least the size of about 1cm, for example, be at least about 2cm, for example, be at least about 4cm, for example, be at least about 6cm, for example, be at least about 8cm, for example, be at least about 10cm, be for example at least the size of about 12cm.In one embodiment, alloy raw material can have at least one and be at least 1 inch, be for example at least 2 inches, be for example at least 3 inches, be for example at least the size of approximately 4 inches.Size herein can refer to any size, such as length, width, thickness, diameter etc.

The alloy raw material of preparing according to method as herein described can be used for manufacturing amorphous alloy, for example bulk amorphous alloys.The method of preparing amorphous alloy is known.For example, in an example, raw material can refuse be melting form, and the formation amorphous alloy that quenches subsequently.The technology of preparing amorphous alloy from alloy crystalline is known, and any known method is used in and manufactures composition herein.Although this paper describes the different examples of formation method, also can use other similar forming processes or its combination.In one embodiment, heating raw materials, to the first temperature of the temperature of fusion Tm higher than raw material interalloy, makes any crystal in alloy all fusible.Then the raw material of heating and melting rapidly cooling (or " quenching ") to the second temperature lower than the Tg of alloy to form foregoing, then can heat said composition to arrange and/or to be shaped.Quench rates and the temperature being heated to can be passed through ordinary method, for example, utilize time-temperature crystal to transform (TTT) figure and determine.The raw material of thin slice, slag ball or any shape providing can have less critical casting thickness, but final parts can have the thickness that is thinner than or is thicker than critical casting thickness.

electronics

Preceding method can be used for manufacturing the raw material that can be used for subsequently preparing BMG.Due to the advantageous characteristic of BMG, BMG can be made into the construction package in multiple equipment and parts.A kind of this type equipment is electronics.

Electronics herein can refer to any electronics known in the art.For example, it can be phone such as mobile phone and fixed line phone, or any communication equipment such as smart phone (comprises for example iPhone ^tM), and equipment is received/sent out to e-mail.It can be a part (for example digital indicator), TV monitor, E-book reader, portable web browser (for example, the iPad of indicating meter ^tM) and computer monitor.It also can be amusement equipment, comprises that Portable DVD player, conventional DVD player, blue light disc player, video game console, for example portable music player of music player are (as, iPod ^tM) etc.It also can be a part for the equipment that control is provided, for example control chart picture, video, sound stream (as, AppleTV ^tM), or it can be the telepilot for electronics.It can be a part for computer or its annex, for example hard disk shell or protective sleeve, laptop computer shell, laptop keyboard, laptop computer rail touch pad, desktop computer keyboards, mouse and loud speaker.These goods can also be applied to the equipment of for example wrist-watch or clock.

Article used herein " one " and " one " refer to the grammar object of one or more than one (, 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 of quoting herein includes end value interior.In the full text of this specification sheets, term " substantially " used and " approximately " are for describing and considering little fluctuation.For example, they can refer to be less than or equal to ± and 5%, be for example less than or equal to ± 2%, be for example less than or equal to ± 1%, be for example less than or equal to ± 0.5%, be for example less than or equal to ± 0.2%, be for example less than or equal to ± 0.1%, be for example less than or equal to ± 0.05%.

Non-limiting working example

ferrous alloy

For comparing, carry out three experiments.The first two experiment is carried out after the scheme of preparing alloy raw material being pre-existing in, and described alloy raw material is used for iron bulk amorphous alloys (Fe subsequently ₄₈cr ₁₅mo ₁₄c ₁₅b ₆y ₂) manufacture, the 3rd experiment used the method for one embodiment of the present of invention description to carry out.Heating and melting is hereinafter described undertaken by arc-melting.Fig. 4 shows for the picture of the element of alloying process and relative dimension (compared with scale) thereof (all have at least one for about 5mm or larger size).

experiment 1

This experiment is prepared the trial of alloy raw material according to following scheme:

(1) melt about 3.1g B (～0.29 mole) and 16.0g Fe (～0.29 mole) to prepare 50-atm%-Fe-50-atm%-B (Fe-B) compound/composition.This step is undertaken by 4 fusings and 3 upsets, and " upset " refers to tumble mixed thing at every turn, to promote before to homogenize in each " fusing ", as mentioned above.

(2) melt about 112.3g Fe, 37.4g Cr, 64.2g Mo formation Fe-Cr-Mo alloy ingot (" button ingot casting ").This step is undertaken by 4 fusings and 3 upsets.Fig. 5 provides the picture of Fe-Cr-Mo alloy.

(3) enter Fe-Mo-Cr to form Fe-Mo-Cr-C composition by FeCrMo ingot bar being placed in to graphite granule top fusing graphite.This step is undertaken by 1 fusing, does not overturn.

(4) make Fe-B compound and the fusing of Fe-Mo-Cr-C composition, attempt formation and there is chemical formula Fe ₄₈cr ₁₅mo ₁₄b ₆y ₂alloy raw material.

result

The atom (or volume) of element is than being set as Mo:C=48:52, Cr:C=50:50, Mo:B=70:30 and Cr:B=71:29.During step (1), Fe and B are found to merge very fast the mutual compound composition of formation adherent metal.Then raise the power of electric arc with composition between complete deposite metal.During power rises to, relatively inhomogeneous prealloy intermetallic composition mixes completely becomes homogeneous, forms fast the melting ingot bar of cavetto.After fusing for the first time and fusing for the second time, can find the flue dust of minimum around intermetallic composition.

During step (2), Fe is easy to fusing and fuses with Mo immediately.Cr is found rapid evaporation, and wherein Cr contacts with electric arc.Compared with pure Fe, the vapour pressure of pure Cr is very high.At electric arc inside furnace, argon pressure is between-10 to-20 inches of mercury.In this " vacuum " level, be easier to Cr evaporation.The wall of electric arc smelting furnace, siege, electrod assembly keep cooling by water coolant.Along with the Cr of evaporation runs into cold surface, it automatically precipitates and applies wall, siege and electrode.Attempt keep Cr away from electric arc, with reduce evaporation and be deposited to equipment compared with cold surface.

Another side effect of this phenomenon is the Cr loss of equipment, causes the Cr concentration of alloy to reduce.If be coated with enough thick Cr layer on electrode, and its sealing or float in the environment of electric arc smelting furnace, can there is electric " short circuit ", it is dangerous.Notice that evaporation is excessive in the time that electric arc (it is similar to the most advanced and sophisticated diffusion flame directly penetrating of tungsten) just in time points to Cr part.For example, in the time that it changes sensing low-vapor pressure element (Mo) into and allows Mo indirect heating Cr, evaporation minimizes.Observe the flue dust lower than desired amount, the Cr that can reach a conclusion should be kept away from electric arc.

During step (3), the Fe-Cr-Mo ingot bar that derives from step (2) is positioned over to the top of carbon (graphite) particle.Found that Fe-Cr-Mo ingot bar breaks, and first ingot bar melts from edge to prevent from scraping.The new ingot bar Fe-Cr-Mo forming is crystallization.Because it is placed on the cold hearth of electric arc smelting furnace, whole ingot bar is very cold.In the time of thermic arc electric current contact ingot bar, thermal shocking causes ingot bar to break.In the time that it breaks, fragment can drop in electric arc smelting furnace Anywhere, causes " composition quality is not good ", " electric short circuit ".Can reach a conclusion preferably first from edge fusing, with breaking of preventing that thermal shocking from causing, and help to search " unfused " piece and make its fusing.Suddenly heating causes bulk part to burst in electric arc smelting furnace in some cases.With regard to Fe-Cr-Mo, ingot bar is also tending towards spontaneous fragmentation when cooling.Be not bound by any theory, but may be because on copper siege cooling rapid enough make thermal shocking also cause ingot bar in the mutual compound fragmentation of friable metal.

Found that as long as ingot bar fusing C part just floats to surface, and C part is luminous and splash and then fade away around surface.Over time, whole ingot bar becomes melting, covers the thin squame rapid flow around on 25-33% surface.Once arc reduction, luminous, apparent immiscible cohesive material drips and swims in ingot bar top.Around electric arc pushes it against, and it is flowed and distortion, but its refusal enter solution.Whether the solution of not testing is the chemical analysis of sosoloid.Observe many flue dust, and the smell burning detected.

During step (4), be positioned over the top of Fe-Cr-Mo-C ingot bar and melt assembly from Y and the Fe-B composition of step (1).Yttrium is found to dissolve and enter ingot bar rapidly, and the dissolving of Fe-B composition is very inadequate, slowly enters ingot bar.After Fe-B fusing, the ingot bar of gained is coated with the squame of undissolved coarse, faceted gradually.

After final ingot bar is cooling, surface is found to become white from lacklustre Dark grey, and has the smell that is similar to metal sewage.In addition, it is found that final ingot bar can not become complete melting between melting period, only has the partial melting region to be found in below coarse squame.In other words, in the time that element mixes in electric arc smelting furnace, one or more compounds form from the teeth outwards, and this compound has the fusing point of maximum temperature～3400 that can bear higher than electric arc smelting furnace DEG C.These high melting compounds can not dissolve subsequently gets back to block button ingot casting, may make ingot bar heterogeneity.In addition, can use arc-melting due to regional area only, the ingot bar in composition is inhomogeneous.

Fig. 6 (a) shows the alloy ingot that derives from experiment 1, wherein separates all crushing members.In crusher surface, can find some spaces and inhomogeneity.Ingot bar is highly brittle, and is broken for multiple when cooling.In addition, the evaporation of some alloy compositions produces volume of smoke, and described flue dust is subsequently cooling rear collection (illustrating on the right) (existing the mensuration of element) in not carrying out flue dust.Test the flue dust of 1 rear collection shown in Fig. 6 (b).The surface of ingot bar is coarse and irregular, and demonstrates the inhomogeneity sign being not exclusively mixed to form during melting process.

In a word, ingot bar is worthless as raw material.

experiment 2

This experiment is prepared the trial of alloy raw material according to following scheme:

(1) melt about 128.1g Fe and about 4.9g C and make 85-atm%-Fe-15-atm%-C (Fe-C) compound/composition (this step is undertaken by the Fe at C top).This step is undertaken by 4 fusings and 3 upsets, and " upset " refers to tumble mixed thing at every turn, to promote before to homogenize in each " fusing " (, melting).

(2) about 3.7g C and the addition of C r, Mo and B are melted, wherein Mo is at the top of B, and B is at the top of Cr, and Cr is at the top of C.Determine Cr～37.3g, Mo～64.2g, B～3.1g according to Inversion Calculation.

(3) Fe-C is positioned over to the top of Fe, Cr, Mo and B, and all these are melted together so that the minimization of loss of Cr.Product is ingot bar.

(4) 0.2g Y is added to the ingot bar that derives from (3), and assembly is melted together.

result

During step (1), Fe slowly melts.In the time contacting with molten pig, carbon arc flicker is green, and molten alloy hisses.In the time that C floats on top, it slowly dissolves and enters solution, jumps around surface.Observe generate appropriate flue dust, most likely due to fizz.Flue dust is found mainly to comprise grey powder.Collect this powder, and add fusing step subsequently.

During step (2), it is found that Mo fusing and fuse with Cr to a certain extent, but a large amount of Cr boiled before mixture solidified.During the step (3), it is found that all mixtures mix and fusing after finally become homogeneous.C part is found to swim in top, and slowly dissolves and enter solution.In addition, in step (2), some Cr evaporate/boil and.In step (3), extra Cr evaporates.Finally, during step (4), Y is found and ingot bar fusion, but it forms immediately thick " top layer ", the extremely difficult fusing in described top layer.It is very difficult melting at once whole ingot bar.In the time boiling, can lose, therefore final composition is no longer correct composition.When two or more elements condense in while forming crystal together, do not obtain homogenizing mixture.In the time of floating or precipitation, do not obtain homogenizing mixture.For this specific iron alloy composite of fusing, Cr and C have provided multiple problems.Even if C swims in top, also slowly dissolve and enter solution.On the other hand, too early if Cr introduces alloy, the evaporation meeting of dissolving needed time durations Cr at C is too much.

Fig. 7 shows the picture of the alloy ingot obtaining in experiment 2.Ingot bar is extremely crisp, and when cooling, is broken into multiple smallclothes.Observed flue dust not as experiment many in 1, but compared with experiment 1 described be still coated with light dust.Compared with experiment 1, in this experiment, even observe more inhomogeneity, surface demonstrates not the evidence on mixed top layer mutually.In a word, ingot bar is worthless as raw material.

experiment 3

This experiment is prepared the trial of alloy raw material according to following scheme:

(1) melt about 12.8g Fe and about 2.5g C and make 50-atm%-Fe-50-atm%-B (Fe-B) compound/composition (this step is undertaken by the Fe at C top).This step be similar to the step (1) of experiment in 1.

(2) by about 98g Fe and approximately 29.8 _gcr, 51.4 _gmo and 6.9 _gy melts, and as shown in Figure 2, forms FeMoCrY.

(3) C is positioned over below every Fe-Mo-Cr-Y, forms their alloy.Product is ingot bar.

(4) make the FeB fusing that step (1) obtains enter the Fe-Mo-Cr-Y part that step (3) obtains, form Fe ₄₈cr ₁₅mo ₁₄b ₆y ₂alloy raw material.

result

During step (1), the result obtaining is similar to those that observe in the step (1) of testing 1.Specifically, element is fusion and viscosity, but after arc-melting power raises formation button ingot casting/ingot bar.

During step (2), Fe is found rapidly and Mo fusion.Referring to Fig. 2.Once Y fusing, material forms heavy squame on its surface, even if this squame does not also melt under superpower.Some mutually a small amount of orange of mixed material be found around surface rollers, even if but under superpower, they are not mixed in ingot bar yet.Ingot bar is fragility, while therefore falling back to siege, can break.Smallclothes are refuse in groove; And during refuse, squame looks more sparse, be almost similar to dissolving.Can reach a conclusion and Fe-Mo-Cr-Y is fused into smaller piece contributes to melting process.Good amorphous alloy is tending towards having good appearance.And massive material is because various factors (high-melting-point top layer, show aobvious immiscible equating) can not melt completely with electric arc, split into smallclothes and separately fusing show that top layer can be dissolved at least partly and enter solution.Be not bound by any theory, but may be because described less quality allows higher temperature of fusion to realize by identical electric arc.After solidifying, Fe-Mo-Cr-Y surface has the facet of blue and brown.

During step (3), C seems slowly accessible dissolving and enters each material pieces.Carbon granule is placed under Fe-Mo-Cr-Y ingot bar, as shown in Figure 3.The quality of each Fe-Mo-Cr-Y part " is fastened " firmly C rod makes it enter cooled region downwards, instead of floats on surface.Carbon is lighter element (low density), and it has the trend that floats on top.If carbon is fastened (that is, catching) in Fe-Mo-Cr-Y below, along with the fusing of mixture, carbon is floating gradually slowly to be dissolved and enters mixture.In the time that it reaches top, most of C dissolves and enters mixture.In addition, because only have local ingot bar region fusible, all the other region effects of ingot bar are similar to solid.Therefore, carbon can not be floating by solid area, and by sticky (or " fastening ") in bottom, even when removing electric arc and generating the melt region on end of carbon-point.Parts under melt region slowly dissolve and enter solution, do not float on top.This makes some discordancies minimize with the effort relevant to the process that C dissolving is entered to alloy.

During step (4), Fe-B composition is at top.After its fusing, initial nonwetting large of composition.Slip away behind surface at it, fuse with the side of Fe-Mo-Cr-Y and start and slowly dissolve and enter block.Along with it becomes more homogeneous, the viscosity of the ingot bar of gained seems less.The product that this experiment obtains comprises that weight is that at least 100g, diameter are the ingot bar of 2-3 inch.After experiment, checking shows that ingot bar can be used as raw material, is the complete amorphous BMG rod of 5mm at least for generation of diameter.

Fig. 8 (a) shows that the little homogeneous crystallization part retaining from ingot bar produces (top) in experiment 3.The copper mould of some part refuses and suction casting Cheng Leng, for generation of the amorphous alloy casting shown in Fig. 8 (a) bottom.Fig. 8 (b) shows the part of the 6mm diameter casting rod of making from refuse and the suction casting part from ferrous alloyization experiment 3.Rod is completely unbodied.Fig. 8 (c) shows the part of the 8mm diameter casting rod of making from refuse and the suction casting part from ferrous alloyization experiment 3.Rod is completely unbodied.

The observation of the alloy bar that the raw material in experiment 3 is made is confirmed by a series of DSC inspections.Fig. 9 (a)-(b) show two respectively from the DSC thermography curve of 6mm and the collection of 8mm casting rod, described casting rod produces from testing 3 raw materials that obtain.Fig. 9 (a) derives from 6mm casting rod, and Fig. 9 (b) shows 6 and the two result of 8mm rod in same figure.The similarity of curve, the especially crystallization event between 600 and 800 DEG C, show that two excellent amorphous contents are actually identical, and they are all completely unbodied.In other words, the alloy ingot that experiment 3 produces approaches required nominal composition very much, and therefore alloying process is considered to successful.

Claims (41)

1. a method of preparing alloy raw material, comprising:

By ferro element and the first non-metallic element are combined to form to the first composition;

By ferro element and multiple transition metal are combined to form to the second composition;

By described the second composition and the second non-metallic element are combined to form to the 3rd composition; And

Make described the first composition and described the 3rd composition alloying to form alloy raw material.

2. method according to claim 1, wherein said the first non-metallic element is B, P, Si, Ge, C or their combination.

3. method according to claim 1, wherein said multiple transition metals comprise Mo, Cr, Ni, Y, Co, Mn, Ga, Er or their combination.

4. method according to claim 1, at least one in wherein said the first non-metallic element and described the second non-metallic element is metalloid.

5. method according to claim 1, wherein said the second non-metallic element is Si, C or the two.

6. method according to claim 1, wherein in the beginning of described the 3rd composition of described formation, described the second non-metallic element is positioned under described the second composition.

7. method according to claim 1, at least some of wherein said element have at least one and are at least the size of about 1mm.

8. method according to claim 1, wherein said alloy raw material is at least one in (i) homogeneous and (ii) not exclusively unbodied.

9. method according to claim 1, wherein said alloy raw material has chemical formula Fe ₄₈cr ₁₅mo ₁₄c ₁₅b ₆y ₂.

10. method according to claim 1, at least a portion of wherein said preparation relates to arc-melting.

Prepare the method for alloy raw material, comprising for 11. 1 kinds:

By iron and the first non-metallic element are combined to form to the first composition;

By iron and multiple transition metal and C are combined to form to carbonaceous composition;

Make described the first composition and described carbonaceous composition alloying to form alloy raw material.

12. methods according to claim 1, wherein said formation carbonaceous composition forms the second composition before being also included in and forming described carbonaceous composition, and described the second composition comprises Mo, Cr, Y, Ni or their combination.

13. methods according to claim 1, wherein said formation carbonaceous composition also comprises by melted alloy and stacks and form the second composition, and described alloy stacks to be had Mo to be arranged at that Fe is upper, Fe is arranged at Cr upper, and Cr is arranged at the stacking order on Y.

14. methods according to claim 13, wherein with respect to the composition that stacks order described in not having, described formation has at least one the lower evaporation in Fe and Cr for described the second composition.

15. methods according to claim 11, wherein said the first composition comprises intermetallics.

16. methods according to claim 11, wherein said alloy raw material is crystallization substantially.

17. methods according to claim 11, wherein said alloy raw material has at least one size of at least 2 inches.

18. methods according to claim 11, also comprise described alloy raw material are prepared into bulk amorphous alloys.

19. methods according to claim 11 are not wherein powder types for element described at least some of described preparation.

20. methods according to claim 11, wherein said the first non-metallic element is B.

Prepare the method for alloy raw material, comprising for 21. 1 kinds:

Provide iron content the first composition;

By C with the second combination of compositions of comprising Mo, Cr and Y to form the 3rd composition; And

By described the first composition and described the 3rd combination of compositions to form alloy raw material.

22. methods according to claim 21, wherein said the first composition is FeB.

23. methods according to claim 21, wherein said the second composition has Mo and is arranged at Fe above, and it is upper that Fe is arranged at Cr, and Cr is arranged at the stacking order on Y.

24. methods according to claim 21, wherein said alloy raw material has at least weight and at least one size of at least 2 inches of 100g.

25. 1 kinds of alloys, comprising:

The first composition that comprises Fe and the first non-metallic element;

The second composition that comprises Fe, multiple transition metal and the second non-metallic element;

Wherein in the first composition described in described alloy and described the second composition alloying.

26. alloys according to claim 25, wherein said the first non-metallic element is B, P, Si, Ge, C or their combination.

27. alloys according to claim 25, wherein said multiple transition metals comprise Mo, Cr, Ni, Y, Co, Mn, Ga, Er or their combination.

28. alloys according to claim 25, at least one in wherein said the first non-metallic element and described the second non-metallic element is metalloid.

29. alloys according to claim 25, wherein said the second non-metallic element is Si, C or the two.

30. alloys according to claim 25, wherein in the beginning of described the 3rd composition of described formation, described the second non-metallic element is positioned under described the second composition.

31. alloys according to claim 25, at least some of wherein said element have at least one and are at least the size of about 1mm.

32. alloys according to claim 25, wherein said alloy is at least one in (i) homogeneous and (ii) not exclusively unbodied.

33. alloys according to claim 25, wherein said alloy has chemical formula Fe ₄₈cr ₁₅mo ₁₄c ₁₅b ₆y ₂.

34. alloys according to claim 25, at least a portion of wherein said preparation relates to arc-melting.

35. alloys according to claim 25, wherein said the second composition comprises the carbonaceous composition that comprises C.

36. alloys according to claim 25, wherein said the second composition also comprises Mo, Cr, Y, Ni.

37. alloys according to claim 36, it is upper that wherein said the second composition comprises that Mo is arranged at Fe, and it is upper that Fe is arranged at Cr, and Cr is arranged at the order that stacks on Y.

38. alloys according to claim 25, wherein said the first composition comprises intermetallics.

39. alloys according to claim 25, wherein said alloy is crystallization substantially.

40. alloys according to claim 25, wherein said alloy has at least one size of at least 2 inches.

41. alloys according to claim 25, wherein said alloy comprises bulk amorphous alloys.