CN1403618A - Bulk amorphous alloy material - Google Patents

Bulk amorphous alloy material Download PDF

Info

Publication number
CN1403618A
CN1403618A CN 01130904 CN01130904A CN1403618A CN 1403618 A CN1403618 A CN 1403618A CN 01130904 CN01130904 CN 01130904 CN 01130904 A CN01130904 A CN 01130904A CN 1403618 A CN1403618 A CN 1403618A
Authority
CN
China
Prior art keywords
alloy
amorphous
crystallization
metal
alloy material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 01130904
Other languages
Chinese (zh)
Other versions
CN1184345C (en
Inventor
魏炳忱
赵德乾
汪卫华
潘明祥
闻平
张志�
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Physics of CAS
Original Assignee
Institute of Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Physics of CAS filed Critical Institute of Physics of CAS
Priority to CNB011309040A priority Critical patent/CN1184345C/en
Publication of CN1403618A publication Critical patent/CN1403618A/en
Application granted granted Critical
Publication of CN1184345C publication Critical patent/CN1184345C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Abstract

The present invention relates to amorphous alloy and the bulk amorphous alloy material is expressed in the formula of [Nd1-xPrx]a-Feb-[Al1-ySiy]c-[Co1-zNiz]d-Cue-Bf-Zrg, where a is 30-90, b is 5-65, c is 5-30, d is 0-40, e is 0-20, f is 0-30 and g is 0-10; and x is 0-1, y is 0-1 and z is 0-1. The material contains at least 50% of amorphous phase. The material of the present invention has low cooling rate, great size and good heat stability, and most of them has hard magnetic performance.

Description

Block non-crystalline alloy material
The present invention relates to Condensed Matter Physics and material science, particularly relate to non-crystaline amorphous metal or metallic glass field.
Metallic glass normally is cooled to the molten metal alloy to solidify formation below the glass transformation temperature and before forming core and crystallization.Common metal and alloy all want crystallization to form crystal when liquid cooled is got off.Yet, had been found that some metal and alloy when rate of cooling is enough fast, the extreme viscid state in the time of when solidifying, can keeping liquid state, thus suppressing crystallization, this rate of cooling need reach p.s. 10 usually 4～10 6The order of magnitude of K.In order to obtain so high rate of cooling, molten metal or alloy can only be sprayed onto on the extraordinary conductive substrate of heat conduction.The alloy of Huo Deing is a non-crystaline amorphous metal like this, but size is very little.Therefore, previously obtd amorphous alloy material all is that molten metal or alloy are ejected into the strip that obtains on the copper roller of high speed rotating, or is cast to the thin slice that obtains in the cold substrate and powder etc.Found non-crystaline amorphous metal recently, so just can utilize lower rate of cooling to suppress crystallization with stronger inhibition crystallizing power.If under very low rate of cooling, can suppress crystallization, then can make larger sized non-crystaline amorphous metal.
It is amorphous ribbon (document 1, W.Klement, R.H.Wilens that Duwez just adopts copper roller quick quenching technique to prepare AuSi as far back as nineteen sixty, and Duwez, Nature, 1960, vol.187, pp869-70), contain subsequently metalloid element (as Si, C, B, Ge, non-crystaline amorphous metal P), particularly ferrous alloy are by big quantity research.But because the amorphous formation ability of most of alloy is very poor, if need be higher than 10 with fast cold preparation 6The rate of cooling of K/s is so the non-crystaline amorphous metal that makes can only be low-dimensional materials dimensionally, as strip, filament, fine powder.Mechanical alloying also once was a method of preparation amorphous powder, and many alloys can change amorphous into by high-energy ball milling, can press amorphous powder in supercooling liquid phase region subsequently and form amorphous block.Yet the density with the block metal glass of this method preparation is relatively poor, and sneaks into other impurity easily.This external irradiation also can make amorphous metalization, as ion implantation etc.What deserves to be mentioned is that the alloy of precious metal element Pt and Pd has higher amorphous formation ability, as PtNiP, PdNiP can pass through B 2O 3Refining repeatedly, obtain diameter 10mm spherical sample (document 2, H.S.Chen, Mater.Sci.Eng., 1976, Vol.23, pp151-54).So obtaining bulk amorphous alloys is the target that scientists is pursued in decades always.
Up to 1989, the Inoue of Japan etc. has found that MgCuY and LaAlNi are that alloy has very high amorphous formation ability (document 3, A.Inoue, T.Zhang, and T.Masumoto, Mater.Trans., JIM, 1989, Vol.30, pp965-72), can prepare millimetre-sized non-crystaline amorphous metal by the copper mold casting, this is to find that first the millimeter level non-crystaline amorphous metal that does not contain precious metal forms system.Alloy systems such as ZrAlNi, ZrAlCu and ZrAlNiCu have been found subsequently again.Succeeded in developing Zr in succession in the U.S. in 1993 and Japan 41Ti 14Cu 12Ni 10Be 23And Zr 65Al 7.5Ni 10Cul 7.5Bulk amorphous alloys (document 4, A.Peker and W.L.Johnson, Appl.Phys.Lett., 1993, Vol.63 PP2342-44), and is used on golf club panel, other precision optical instrument parts, corrosion-resistant vessel, bullet or the armour piercing shot bullet core very soon.Discover that in addition bulk amorphous alloys has the superplastic deformation ability in supercooling liquid phase region, therefore moulding and the processing for alloy provides possibility.
People such as the He of the U.S. have reported Nd base bulk-metallic glass the earliest in 1994, they have prepared several five yuan of amorphous with the metal mold method, overall dimension is about 6mm (document 5, Y.He, C.E.Price, S.J.Poon and G.J.Shiflet, Phil.Mag.Lett., 1994, Vol70, PP371-377).It is bulk-metallic glass (BMG) (document 6, A.Inoue, A.Takeuchi and T.Zhang that the method for inhaling casting to 1996～1997 years humans such as Inoue has been prepared the Nd-Fe-Al that overall dimension can reach φ 15mm, Metall.Mater.Trans., 1998, Vol.29A, PP 1770-1793).Nd-Fe-Al is that the discovery of BMG has caused concern widely very soon, and it is a special case in the bulk-metallic glass system, has two characteristics that are different from all other bulk-metallic glass systems.At first, this material shows hard magnetic in room temperature, and coercive force is about 300KAm -1BMG is the large block amorphous new Application Areas of having opened up as a kind of retentive material Nd of high-coercive force base, as at magnetic recording material, and magneto-optic element, aspects such as permanent magnet and excitation material are with a wide range of applications.
Amorphous alloy has huge practicality aspect ferromegnetism, this also is one of important impellent of amorphous material development.Amorphous alloy is existing wide application field aspect soft magnetic material.These amorphous soft magnetic materials are divided three classes by the unusual of its composition: (1) rare earth-transition metal series (RE-TM); (2) transition metal-metalloid system (TM-M); (3) transition metal-metal system (TM-MT).Transition metal iron, cobalt, nickel are principal element in this three classes non-crystalline material, generally account for 70～90%.This class alloy will form non-crystalline state needs very high speed of cooling, is generally 10 4～10 6K/s.Can only be prepared into low-dimensional materials, as strip, filament and powder etc., minimum unidimensional yardstick is generally less than 40～60 microns, band most importantly wherein, and thickness is generally 25～40 microns.These amorphous Fe magneticsubstances have several still unsolved shortcomings at present, have influenced the performance advantage of finished product and application widely: the one, and band is thinner, and this has increased the lamination number of plies unshakable in one's determination and has reduced stacking factor; The 2nd, annealing embrittlement, the amorphous thermostability of traditional non-crystalline material is low, and crystallization is difficult to control, has caused the fragility of material, the choice of having reduced design and having made.The a series of non-crystalline materials that provide among the present invention can be prepared into the bulk amorphous material that smallest dimension is of a size of 100 microns to 15 millimeters, and its magnetic property mainly shows as hard magnetic.In its chemical ingredients, transition metal Nd and Pr are principal element, account for 30～90%.Aspect thermostability, similar with Zr base large amorphous alloy material, the base block amorphous attitude alloy of this Nd (Pr) has high hot temperature, crystallization does not take place, the ratio (T of the crystallization temperature of some compositions and fusing point in the very wide temperature range more than being heated to glass transformation temperature x/ T m) approach 0.9.High like this ratio shows that the base amorphous material of Nd (Pr) has very high thermostability.The hard magnetic amorphous alloy of this block has marked difference with traditional amorphous Fe magneticsubstance on composition, performance and yardstick, also opened up new application prospect for the application of amorphous material.
But the formation of non-crystaline amorphous metal always faces a kind of like this difficulty, crystallization always when promptly the alloy melt of high undercooling solidifies.Crystallization is finished by forming core and crystal growing process.In general, the supercooled liquid crystallization is very fast.Form the non-crystaline amorphous metal solid, must be with the mother alloy liquation from temperature of fusion T mBe cooled to glass transformation temperature T gBelow and crystallization can not take place.
The object of the present invention is to provide a series of block non-crystalline alloy materials, can use following formulate: [Nd 1-xPr x] a-Fe b-[Al 1-ySi y] c-[Co 1-zNi z] d-Cu e-B f-Zr gWherein the variation range of a, b, c, d, e, f, g is respectively: 30≤a≤90,5＜b＜65,5≤c≤30,0≤d≤40,0≤e≤20,0≤f≤30,0≤g≤10; The variation range of x, y, z is: 0≤x≤1,0≤y≤1,0≤z≤1.This material need comprise the glassy phase or the amorphous phase of at least 50% volume percent.The rate of cooling of material of the present invention is low, and size is not less than 100 microns in each dimension.
The object of the present invention is achieved like this:
Fig. 1 is the heat content of typical non-crystaline amorphous metal and the curve of temperature, and wherein curve a is the logarithmic curve of temperature and time, and fusing point T is understood in the figure acceptance of the bid mWith glass transformation temperature T g, the front end of curve has been represented and has been separated out the given required shortest time of crystal volume fraction.In order to obtain a kind of unordered solid material, alloy must be from cooling down by glass transition more than the fusing point and crystallization not taking place, promptly alloy when fusing point cools down by glass transformation temperature can not with the crystallization curve intersection.Crystallization curve a has represented the crystallization behavior of the non-crystaline amorphous metal that very early time obtains, and its rate of cooling has surpassed 10 5K/s is usually 10 6The order of magnitude of K/s.Curve b is the crystallization curve of the non-crystaline amorphous metal developed afterwards, forms the needed rate of cooling of non-crystaline amorphous metal and has reduced by 1 or 2 even 3 order of magnitude.Curve c is the crystallization curve of the non-crystaline amorphous metal done of the present invention, and required rate of cooling further greatly reduces, and rate of cooling is no more than per second 10 2K.
Amorphous alloy material provided by the invention can be used following formulate: [Nd 1-xPr x] a-Fe b-[Al 1-ySi y] c-[Co 1-zNi z] d-Cu e-B f-Zr g, wherein a, b, c, d, e, f, g are atomic percent, and its variation range is: 30≤a≤90,5＜b＜65,5≤c≤30,0≤d≤40,0≤e≤20,0≤f≤30,0≤g≤10; X, y, z are atomic fraction, and its variation range is: 0≤x≤1,0≤y≤1,0≤z≤1.
Listed several transition metals, any other transiting group metal elements of common 5% to 10% all is acceptable in non-crystaline amorphous metal in formula.And non-crystaline amorphous metal allows to contain a spot of impurity (for example, a spot of oxygen may be dissolved in the non-crystaline amorphous metal and significant crystallization can not take place, and also may contain other subsidiary element), but the total amount of impurity should be less than 5% (atomic percent).The interpolation (as: a spot of molybdenum, manganese, chromium, niobium, vanadium, hafnium, germanium, phosphorus, carbon, nitrogen etc.) of trace element can improve or reduce the magnetic property of material, and the total amount of these elements should be less than 10%.With the specific magnetising moment that Nd in a spot of heavy rare earth element (as Sm, Gb, Td, Eu, Dy, Er) equivalent material or Pr can improve alloy, improve other magnetic property, and do not significantly improve the cost of material.
The method that various expression alloying constituents are arranged, above-mentioned equation expression are wherein a kind of.In equation expression, generally express the shared ratio of various elements with algebraically, this ratio is complementary.Some occupies a high proportion of element that can keep amorphous phase can overcome the tendency that other element promotes crystallization, can improve the amorphous formation ability of rare earth element-transition metal system as element aluminum and silicon, improves the out to out of non-crystalline material.
For realizing purpose of the present invention, material of the present invention need comprise the glassy phase or the amorphous phase of at least 50% volume percent.
Can use traditional method for preparing non-crystaline amorphous metal to obtain amorphous alloy material of the present invention.Get rid of preparation band, paper tinsel and thin slices such as band or two rolling sheets as single roller.Specific implementation is as follows:
The present invention can adopt profuse technical pure rare earth element nd of domestic reserves and Pr, prepares a series of basic bulk-metallic glass of Nd (Pr) that are suitable for domestic resources characteristic and are easy to the technology realization.
With 1～100K/s or lower rate of cooling cooling, the scantling of preparing is not less than 100 microns in each dimension with uniform alloy melt.Such rate of cooling can realize by multiple technologies: as the cold copper mold of alloy casting water inlet being obtained being of a size of 1～10 millimeter or bigger tabular, bar-shaped, strip or mesh members; Also can in quartz container, carry out cold quenching, obtain 15 millimeters or larger sized bar-shaped sample; Can also single roller get rid of methods such as band method or two rolling sheets and directly prepare thickness greater than 100 microns band or thin slice.
1) water quenching: purity is not less than 99.8% Nd, Pr, Al, Fe, Ni, Co, Cu, B, Si, Zr by required atom proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix, cooling obtains mother alloy ingot.These ingot castings are packed into by pulverizing in the quartz glass tube, and vacuum is extracted into 10 -1Encapsulate behind the Pa, in stove, be heated to 850 ℃ and keep making the ingot casting remelting in 10 minutes, the shrend then, [Nd of acquisition uniform ingredients 1-xPr x] a-Fe b-[Al 1-ySi y] c-[Co 1-zNi z] d-Cu e-B f-Zr gColumn bulk alloy, the alloy diameter can reach φ=10mm.
2) teeming practice: purity is not less than 99.8% Nd, Pr, Al, Fe, Ni, Co, Cu, B etc. by needed atom proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix, cooling obtains mother alloy ingot.With melting in high frequency furnace after the mother alloy ingot fragmentation, the vacuum tightness of high frequency furnace vacuum chamber is not less than 10 then -1Pa, the fusing back is blown in the water cooled copper mould with argon gas.
3) vacuum suction casting technique: purity is not less than 99.8% Nd, Pr, Al, Fe, Ni, Co, Cu, B etc. by needed atom proportioning arc melting in the argon atmospher of titanium absorption, make it to mix, this electric arc furnace has absorbing and casting device, and alloy is injected copper mold.
4) single roller gets rid of the band method: purity is not less than 99.8% Nd, Pr, Al, Fe, Ni, Co, Cu, B etc. by needed atom proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix, cooling obtains mother alloy ingot.Get rid of in the belting in vacuum then, under vacuum atmosphere or argon shield atmosphere, blow on the copper roller rotating, get rid of into strip with argon gas.Thickness, width and the structural state of the parameter control bands that obtain such as the rotating speed by changing the copper roller, the flow of molten alloy and temperature.
5) case of flux methods: purity is not less than 99.8% Nd, Pr, Al, Fe, Ni, Co, Cu, B etc. by required atom proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix, cooling obtains mother alloy ingot.Make fusing assistant with the boron trioxide powder after the roasting oven dry, together pack in the quartz glass tube with the mother alloy of pulverizing, weight ratio is 2: 5 to 3: 5.Vacuum is extracted into 10 -1Encapsulate behind the Pa, in stove, be heated to 850 ℃ of slowly coolings then, heat so repeatedly 3～10 times, at last in 850 ℃ of insulations 10 minutes, shrend then.
The amorphous phase proportion can be estimated by differential thermal analysis, the heat content of release was compared when method was the heat content that discharges during with the heating of complete amorphous sample with partially-crystallized sample heating, its ratio can provide amorphous phase shared molar fraction in raw sample, can also determine the ratio of its amorphous phase in non-crystaline amorphous metal with tem study (TEM).The difference that non-crystalline material shows in the electron microscopic analysis method is very little, and the material of crystallization just has very big difference, and is easy to difference.Can differentiate phase with the method for transmission electron diffraction (TED) then.The volume fraction of the non-crystalline material in the sample also can be estimated with the transmission electron microscopy image.
Amorphous phase in the non-crystaline amorphous metal can verify by many currently known methodss.The X-ray diffractogram of non-crystaline amorphous metal has shown the scattering peak of a wide disperse fully.In non-crystaline amorphous metal, contain the crystallization phase time, will observe the Bragg diffraction peak of sharp-pointed relatively representative crystallization phase.Fig. 2 to Fig. 4 is the X-ray diffraction analysis figure of several non-crystaline amorphous metals of the present invention listed in the table 1, as seen from the figure, in the effective resolution of X-ray diffractometer, do not observe tangible crystallization peak, be mainly the scattering peak of wide disperse in the diffraction spectra, illustrate that amorphous accounts for main main body in the prepared alloy.
Table 1 is can be with obtain bar-shaped of water quenching, teeming practice and vacuum suction casting technique and the detail tabulation of getting rid of the band alloy that the band method obtains, at least 100 microns of the diameters of these alloys or bigger, and amorphous phase accounts for 50% at least.The performance of these alloys is also listed in the table, comprises the crystallization temperature (T that represents with absolute temperature x), fusing point (T m) and some magnetic properties, as saturation magnetization (M s), residual magnetization (M r) and coercive force (H c), its temperature measurement technology is differential thermal analysis (DSC).Crystallization temperature is the heating rate of non-crystaline amorphous metal sample with per minute 10K to be heated to more than the glass transformation temperature enthalpy change temperature indicative when crystallization of record begins.
Most of non-crystaline amorphous metal provided by the invention has high-coercive force, and its value and alloying constituent and preparation technology are closely related.Most of near or surpass 3000 oersteds.Can see that from table 1 crystallization temperature of most alloys surpasses 700K, this illustrates that they have good thermostability.The critical cooling rate of non-crystaline amorphous metal provided by the invention under no crystallization situation be all at 1～100K/s, can form minimum unidimensional scale and be 100 microns to 15 millimeters bulk amorphous alloy material, shows that they all have good amorphous formation ability.With several preparation methods of the present invention, can both obtain to surpass 100 microns non-crystalline material, overall dimension can reach 15 millimeters.
The present invention will be further described below in conjunction with drawings and Examples:
Fig. 1 is the heat content of typical non-crystaline amorphous metal and the curve of temperature,
Fig. 2～Fig. 4 is the X-ray diffractogram of non-crystaline amorphous metal of the present invention,
Fig. 5 is heat analysis (DSC) curve of several non-crystaline amorphous metals of the present invention,
Fig. 6 be several φ 3mm non-crystaline amorphous metal casting rod of the present invention the room temperature magnetic hysteresis loop.
Embodiment 1:
With purity be 99.9% to 99.99% Nd, Al, and Fe by needed atom proportioning arc melting in the argon atmospher of titanium absorption, make it to mix, cooling obtains ingot casting.With melting in high frequency furnace after the mother alloy ingot fragmentation, the vacuum tightness of high frequency furnace vacuum chamber is not less than 10 then -1Pa, the fusing back is blown in the water cooled copper mould with argon gas, and the composition of the bulk amorphous alloys of preparing is Nd 65Al 10Fe 25, diameter is 3 millimeters.X ray and transmission electron microscope confirm to be mainly amorphous phase.Can record its crystallization temperature (T from the DSC curve x) and temperature of fusion (T m).The fusing point T of this alloy mBe 875K, crystallization temperature T xBe 814K, T xAnd T mRatio reach 0.93, show that alloy has high thermostability.The coercive force of this alloy is 3400 oersteds, and saturation magnetization is 10.3emu/g, and residual magnetization is 8.2emu/g, and remanence ratic is 0.8, shows that its magnetic hysteresis loop has good rectangle degree.
Embodiment 2:
Technical scheme such as embodiment 1, the composition of the bulk amorphous alloys of preparing are Nd 60Al 10Fe 20Co 10This alloy is at Nd 65Al 10Fe 25In the alloy, obtain with alternative Fe of Co and Nd.The adding of Co has reduced the fusing point of alloy, has improved the amorphous formation ability of alloy, makes alloy have higher and better manufacturability.The fusing point T of this alloy mBe 783K, crystallization temperature T xBe 771K, T x/ T mValue is 0.98, illustrate that its amorphous has higher thermostability than embodiment 1 the large block amorphous of preparation, but the absolute value of crystallization temperature descends to some extent.The coercive force of this alloy is 3410 oersteds, is higher than the coercivity value of embodiment 1, and specific magnetising moment value is close.
Embodiment 3
With purity be 99.9% to 99.99% Nd, Al, and Fe by needed atom proportioning arc melting in the argon atmospher of titanium absorption, make it to mix, cooling obtains ingot casting.These ingot castings are packed into by pulverizing in the quartz glass tube, pumping high vacuum (10 -1Pa) back encapsulation makes the ingot casting remelting in stove, shrend then, the Nd of acquisition uniform ingredients 65Al 10Fe 25Column bulk alloy, diameter are 5 millimeters, and the coercive force of this alloy is 3380 oersteds, and saturation magnetization is 10.9emu/g, and remanent magnetism is 8.3emu/g.The magnetic property of its magnetic property and the resultant material of embodiment is very approaching.
Embodiment 4
With purity be 99.9% to 99.99% Nd, Al, Fe and Co by needed atom proportioning arc melting in the argon atmospher of titanium absorption, make it to mix, cooling obtains ingot casting.To get rid of remelting in the band machine in vacuum after the mother alloy ingot fragmentation then, the vacuum tightness that vacuum is got rid of band machine vacuum chamber is not less than 10 -1Pa, it is 6m/s (linear velocity) copper roller surface that the fusing back blows to rotating speed with argon gas, prepares the band that thickness is about 120 microns, composition is Nd 60Al 10Fe 20Co 10X ray and transmission electron microscope confirm to be mainly amorphous phase.The coercive force of this material is 1300 oersteds, and saturation magnetization is 15emu/g, and remanent magnetism is 5.7emu/g, and remanence ratic is 0.38.As seen use this technical scheme, the non-crystalline material of acquisition has tangible difference with performance with embodiment 2 materials of sample ingredient on performance, and coercive force significantly reduces, and hard magnetic weakens, but saturation magnetization obviously increases.The rectangle degree of magnetic hysteresis loop significantly worsens.
Embodiment 5
Technical scheme such as embodiment 4, the composition of the bulk amorphous alloys of preparing are Nd 40Al 10Fe 50This alloy is less a kind of of various amorphous alloy component middle-weight rare earths constituent content provided by the invention.Comparing with the composition of embodiment 1, mainly is to have substituted rare earth element nd with Fe.The fusing point fusing point that substitutes the back alloy significantly improves T mBe 954K, crystallization temperature T xAlso bring up to 760K.Saturation magnetization sharply is increased to 38.9emu/g, and remanent magnetism is increased to 10.2emu/g, and coercive force significantly is reduced to 420 oersteds, and hard magnetic property disappears.Behind the alternative rare earth element of transition metal, the cost of material obviously reduces, and the specific magnetising moment significantly improves, but coercive force decline, hard magnetic property constantly weakens.
Embodiment 6
Technical scheme such as embodiment 1, the composition of the bulk amorphous alloys of preparing are Nd 60Al 10Co 30The crystallization temperature of this alloy is 552K, and fusing point is 798K.This alloy has fusing point and the crystallization temperature lower than embodiment 1, T x/ T mRatio is 0.69.Thermostability reduces.This alloy does not have hard magnetic property, shows as paramagnetism in room temperature.
Table 1
Composition  T m(K)  T x(K)  H c(Oe)     M s  (emu/g)    M r  (emu/g)
 Nd 65Al 10Fe 25  875  814  3400   10.3  8.2
 Nd 80Al 10Fe 10  866  757  1890   4.8  1.7
 Nd 40Al 10Fe 50  954  760  420   38.9  10.2
 Nd 60Al 10Co 30  798  552
 Nd 70Al 10Co 20  801  549
 Nd 60Al 15Ni 10Cu 15Co 5  725  470
 Nd 6Al 15Ni 10Cu 10Fe 5  710  475
 Nd 65Al 10Fe 20Co 5  787  768  3010   10.4  6.5
 Nd 65Al 10Fe 20B 5  882  784  2950   9.8  5.9
 Nd 65Al 10Fe 20Cu 5  873  810  3100   5.9  5.5
 Nd 65Al 10Fe 20Ni 5  873  813  3250   7.6  7.0
 Nd 45Al 10Fe 25Cu 20  730  458
 Nd 50Al 30Fe 20  797  718  2940   8.4  6.3
 Nd 60Al 10Ni 30  790  648
 Nd 65Al 10Fe 15Co 10  787  758  3520   7.1  6.4
 Nd 65Al 10Fe 10Co 15  787  720  3605   5.0  4.8
 Nd 60Al 10Fe 20Co 10  783  771  3410   10.5  7.6
 Nd 60Al 10Fe 20Co 5Si 5  802  748  3250   8.4  5.7
 Nd 50Al 10Fe 20B 20  918  810
 Pr 60Al 10Fe 30  859  771  3640   9.6  7.8
 Pr 70Al 10Fe 20  856  758  2660   5.0  3.5

Claims (4)

1. block non-crystalline alloy material is characterized in that: use following formulate: [Nd 1-xPr x] a-Fe b-[Al 1-ySi y] c-[Co 1-zNi z] d-Cu e-B f-Zr gWherein a, b, c, d, e, f, g are atomic percent, and its variation range is respectively: 30≤a≤90,5＜b＜65,5≤c≤30,0≤d≤40,0≤e≤20,0≤f≤30,0≤g≤10; X, y, z are atomic fraction, and its variation range is respectively: 0≤x≤1,0≤y≤1,0≤z≤1.
2. by the described block non-crystalline alloy material of claim 1, it is characterized in that: any transiting group metal elements or the heavy transition metal that also can contain 5% to 10% atomic percent.
3. by the described block non-crystalline alloy material of claim 1, it is characterized in that: also can contain total amount and be less than 5% atomic percent impurity.
4. by the described block non-crystalline alloy material of claim 1, it is characterized in that: the amorphous phase that need comprise at least 50% volume percent.
CNB011309040A 2001-08-24 2001-08-24 Bulk amorphous alloy material Expired - Fee Related CN1184345C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB011309040A CN1184345C (en) 2001-08-24 2001-08-24 Bulk amorphous alloy material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB011309040A CN1184345C (en) 2001-08-24 2001-08-24 Bulk amorphous alloy material

Publications (2)

Publication Number Publication Date
CN1403618A true CN1403618A (en) 2003-03-19
CN1184345C CN1184345C (en) 2005-01-12

Family

ID=4670228

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB011309040A Expired - Fee Related CN1184345C (en) 2001-08-24 2001-08-24 Bulk amorphous alloy material

Country Status (1)

Country Link
CN (1) CN1184345C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104321838A (en) * 2012-02-23 2015-01-28 吉坤日矿日石金属株式会社 Neodymium-based rare-earth permanent magnet and process for producing same
CN106504867A (en) * 2017-01-05 2017-03-15 海安县申菱电器制造有限公司 A kind of amorphous alloy transformer and amorphous alloy strips preparation method
CN111593274A (en) * 2020-05-26 2020-08-28 湖南理工学院 A series of zirconium-base amorphous alloys with special crystallization behavior

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104321838A (en) * 2012-02-23 2015-01-28 吉坤日矿日石金属株式会社 Neodymium-based rare-earth permanent magnet and process for producing same
CN104321838B (en) * 2012-02-23 2018-04-06 吉坤日矿日石金属株式会社 Neodymium base rare earth element permanent magnet and its manufacture method
US9972428B2 (en) 2012-02-23 2018-05-15 Jx Nippon Mining & Metals Corporation Neodymium-based rare earth permanent magnet and process for producing same
CN106504867A (en) * 2017-01-05 2017-03-15 海安县申菱电器制造有限公司 A kind of amorphous alloy transformer and amorphous alloy strips preparation method
CN106504867B (en) * 2017-01-05 2019-04-26 海安县申菱电器制造有限公司 A kind of amorphous alloy transformer and amorphous alloy strips preparation method
CN111593274A (en) * 2020-05-26 2020-08-28 湖南理工学院 A series of zirconium-base amorphous alloys with special crystallization behavior

Also Published As

Publication number Publication date
CN1184345C (en) 2005-01-12

Similar Documents

Publication Publication Date Title
Luborsky Amorphous metallic alloys
Inoue et al. Bulk Nd–Fe–Al amorphous alloys with hard magnetic properties
Zhang et al. Bulk nanocomposite permanent magnets produced by crystallization of (Fe, Co)–(Nd, Dy)–B bulk glassy alloy
CN101256859A (en) Rare-earth alloy casting slice and method of producing the same
CN106756644B (en) A kind of iron-based amorphous and nanocrystalline soft magnetic alloy and preparation method thereof based on element silicon
US6280536B1 (en) Fe based hard magnetic alloy having super-cooled liquid region
CN110541116B (en) Crystallization-controllable iron-based nanocrystalline magnetically soft alloy
CN101215679A (en) Nonmagnetic iron-base block amorphous alloy and preparation method thereof
Masood et al. Effect of Ni-substitution on glass forming ability, mechanical, and magnetic properties of FeBNbY bulk metallic glasses
Lee et al. Excellent thermal stability and bulk glass forming ability of Fe-B-Nb-Y soft magnetic metallic glass
Inoue et al. Soft magnetic properties of nanocystalline Fe-Si-B-Nb-Cu rod alloys obtained by crystallization of cast amorphous phase
Kılıçaslan et al. Effect of Fe-Ni substitution in FeNiSiB soft magnetic alloys produced by melt spinning
US4983230A (en) Platinum-cobalt alloy permanent magnets of enhanced coercivity
CN1184345C (en) Bulk amorphous alloy material
Tan et al. Magnetic properties of Fe–Co–Nd–Y–B magnet prepared by suction casting
CN1250762C (en) Praseodymium base massive non-crystalline alloy with permanent magnetism
Makino et al. Fe-metalloids bulk glassy alloys with high Fe content and high glass-forming ability
JP4320701B2 (en) Permanent magnet alloy and bonded magnet
JP3299887B2 (en) Hard magnetic material
Zhang et al. Thermal stability and soft magnetic properties of (Fe, Co)-(Nd, Dy)-B glassy alloys with high boron concentrations
CN1514035A (en) Iron base large block non crystalline alloy
Harada et al. Crystallization of amorphous melt-spun Nd15Fe77Bx (x= 6–14) alloys
JP4043613B2 (en) Fe-based hard magnetic alloy with supercooled liquid region
Wang et al. Improving the B s and soft magnetic properties of Fe-based amorphous ribbons by manipulating the surface crystallization behavior
US20070258846A1 (en) Nd-based two-phase separation amorphous alloy

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee