CN102776452A - Iron-based amorphous alloy material with high glass-forming capability - Google Patents

Iron-based amorphous alloy material with high glass-forming capability Download PDF

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CN102776452A
CN102776452A CN2012103045768A CN201210304576A CN102776452A CN 102776452 A CN102776452 A CN 102776452A CN 2012103045768 A CN2012103045768 A CN 2012103045768A CN 201210304576 A CN201210304576 A CN 201210304576A CN 102776452 A CN102776452 A CN 102776452A
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alloy
amorphous alloy
alloy material
amorphous
based amorphous
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陈庆军
刘江烈
周贤良
沈军
华小珍
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Nanchang Hangkong University
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Abstract

An iron-based amorphous alloy material with high glass-forming capability consists of the elements of Fe, Cr, Mo, C, B, Y and Co, wherein the atomic number ratio of the Fe, Cr, Mo, C, B, Y and Co are (24-32%):(16-24%):15%:14%:15%:6%:2%; the atomic number ratio of the elements of Fe, Cr, Mo, C, B, Y and Co are 24%:24%:15%:14%:15%:6%:2%; the atomic number ratio of the elements of Fe, Cr, Mo, C, B, Y and Co are 28%:20%:15%;14%:15%:6%:2%; and the atomic number ratio of the elements of Fe, Cr, Mo, C, B, Y and Co are 32%:16%:15%:14%:15%;6%:2%. The iron-based amorphous alloy material not only has a simple preparation technology, is low in cost, but also has good amorphous-forming capability and glass-forming capability, and also has mechanical properties with high strength and high hardness.

Description

The Fe-based amorphous alloy material of high glass forming ability
Technical field
The present invention relates to Materials science and Condensed Matter Physics field, relate in particular to a kind of Fe-based amorphous alloy material of high glass forming ability.
Background technology
Metallic glass normally is cooled fast to glass transformation temperature to the molten metal alloy, do not solidify before the forming core at alloy to form, and metal generally to get off from liquid cooled all be that the forming core crystallization forms crystal.In order to obtain very high rate of cooling, as long as molten metal is sprayed onto in the extraordinary substrate of thermal conductivity with better formation amorphous alloy.Yet; Have been found that some alloy when speed of cooling is enough fast, the viscous state in the time of when solidifying, also can keeping liquid state, thus can suppress crystallization; In order to obtain very high rate of cooling; Melted alloy is directly inhaled casting in the good substrate of thermal conductivity, and previously obtd alloy all is a strip, powder etc.If under very low speed of cooling, can suppress crystallization, then can obtain the bigger non-crystaline amorphous metal of size.Duwez just adopts quench to prepare AuSi in nineteen sixty to be amorphous ribbon, the non-crystaline amorphous metal of metalloid is arranged again subsequently, and particularly Fe-based amorphous alloy is by big quantity research.Here we preparation method of employing is the arc melting copper mold casting method, and copper mold casting method is that the preparation block amorphous alloy is the most frequently used, a kind of method of most convenient.This method preparation have aspect dystectic block amorphous alloy additive method the unique advantage that can not compare.Its basic principle of work is: under inert atmosphere, use the electric arc master alloy melting; After the mother alloy fusing; Utilize the suction that different air pressure produced between melt chamber and the copper mold then; The alloy of fusing is sucked in the copper mold of recirculated water cooling, utilize water cooled copper mould heat conduction to realize cooling fast, to obtain block amorphous alloy.Because the rate of cooling of copper mold is limited, so the size of the block amorphous alloy that can prepare is also limited.Along with the increase of alloy size, form the required rate of cooling of non-crystaline amorphous metal and also sharply increase.When the size of sample increased to certain size, copper mold also just can not satisfy block amorphous alloy and form required cooling conditions.Yet because the amorphous formation ability of most of alloy is limited, and the speed of cooling that requires is higher than 10 6K/s is so the non-crystaline amorphous metal of a lot of preparations is strip, filament etc. on basically.So obtaining the large size non-crystaline amorphous metal in lower speed of cooling is the target that scientist pursues always.
1989, it was that alloy has very high amorphous formation ability that the Inoue etc. of Japan has invented MgCuY, prepared millimetre-sized non-crystaline amorphous metal through the copper mold casting, and this alloy do not contain precious metal, had found the ZrAlNiCu system subsequently again.And be applied to precision optical instrument very soon, on the corrosion-resistant vessel, discover that bulk amorphous alloys has the superplastic deformation ability in supercooling liquid phase region, this for the shaping of non-crystaline amorphous metal and processing provide maybe.Fe-based amorphous alloy is with a long history; And also be that application is the widest at present; But the developing history of Fe-based amorphous alloy is shorter; Main thin ribbon shaped product through the flash set technology preparation before 1993, for further preparation has Fe-base noncrystal alloys such as good mechanical property, corrosion resistance nature and magnetic performance, Akihisa Inoue study group adopted metallic copper die cast method to prepare the Fe that thickness is 0.1mm first in 1993 75Si 10B 15Non-crystaline amorphous metal; Obtained the breakthrough achievement of Fe-based amorphous alloy bulkization; Along with deepening continuously to large block amorphous formation ability and thermostability Study on influencing factors; Especially have the foundation than three principle of experience of composition design of large-amorphous forming capacity alloy, nineteen ninety-five has successively found to have bigger supercooling liquid phase region (△ T x) and reduction glass transformation temperature (T Rg) promptly having the more Fe-base alloy system of large-amorphous forming capacity, nineteen ninety-five has successively been found △ T xFe greater than 60K 72Al 5M 2P 11C 6B 4(M=Ga or Ge) alloy, the Fe that calendar year 2001 develops 30Co 30Ni 15Si 18B 17Non-crystaline amorphous metal has the reduction glass transformation temperature up to 0.65.At present by molten metal through copper mold or shrend directly the typical Fe-base large amorphous alloy system of preparation mainly contain Fe-Co-Ln-B (Ln=lanthanon), Fe-(Cr, Mo, Nb, Ta)-(P, C, B) and Fe-Si-B-(Nb, Cu Zr) wait the △ T of these several types of alloys xGenerally all greater than 50K.Amorphous alloy material is one type of type material, compares with common crystal alloy material, and the variation that showing has all taken place in mechanics, physics, chemical property and mechanical properties amorphous alloy material.Non-crystaline amorphous metal faces some problems when forming; When being set in high undercooling, alloy melt is easy to take place crystallization; And crystallisation process will have forming core and crystal growth process, and the supercooled liquid crystallization is very fast, so want to form non-crystaline amorphous metal; We must be cooled fast to the alloy liquation below the Tg, thereby can better stop alloy generation crystallization.Forming non-crystaline amorphous metal only is the prelude that obtains bulk amorphous alloys, and its less important reduction prepares the cost of non-crystaline amorphous metal, makes it can access better application.Adopt the iron-base amorphous alloy material of the high glass forming ability of feedstock production of technical purity, obtain having the non-crystaline amorphous metal and the good processing properties of big three-dimensional dimension.Non-crystaline amorphous metal has the performance of a lot of excellences in supercooling liquid phase region, is easier to take place crystallization at this regional non-crystaline amorphous metal ratio, is very important so select a suitable liquid phase region temperature processing non-crystaline amorphous metal.Here our rate of cooling of expecting to form non-crystaline amorphous metal is from per second 10 3Be as cold as to 1K/s or lower rate of cooling, do not take place at non-crystaline amorphous metal under the situation of crystallization, process more than can being heated to the glass transition point temperature to non-crystaline amorphous metal fully, make it can be used for industry better.
Summary of the invention
The object of the present invention is to provide the Fe-based amorphous alloy material of the high glass forming ability of a kind of HS, high firmness.
The present invention realizes like this; A kind of Fe-based amorphous alloy material of high glass forming ability; It is characterized in that it is elementary composition by Fe, Cr, Mo, C, B, Y and Co, press following atom number proportioning: Fe 24 ~ 32%, Co 16 ~ 24%, Cr 15%, Mo 14%, C 15%, B 6%, Y 2%; Said Fe, Cr, Mo, C, B, Y and Co element by atom number ratio are: Fe 24%, Co 24%, Cr 15%, Mo 14%, C 15%, B 6%, Y 2%; Said Fe, Cr, Mo, C, B, Y and Co element by atom number ratio are: Fe 28%, Co20%, Cr 15%, Mo 14%, C 15%, B 6%, Y 2%; Said Fe, Cr, Mo, C, B, Y and Co element by atom number ratio are: Fe 32%, Co16%, Cr 15%, Mo 14%, C 15%, B 6%, Y 2%; The purity of said Fe, Cr, Mo, C, B, Y and Co is 99.7% to 99.9%.
Technique effect of the present invention is: Fe-based amorphous alloy material of the present invention not only preparation technology is simple, and production cost is low, and has good amorphous formation ability and glass forming ability, also has the mechanical property of HS, high firmness.
Description of drawings
Fig. 1 is part block amorphous alloy 2 * 13mm of the present invention 2The tabular X-ray diffractogram of thickness * width.
Fig. 2 is heat analysis (DSC) curve (a) of part amorphous alloy material of the present invention.
Fig. 3 is heat analysis (DSC) curve (b) of part amorphous alloy material of the present invention.
Fig. 4 is Fe 41Co 7Cr 15Mo 14C 15B 6Y 2(Fe41), Fe 28Co 20Cr 15Mo 14C 15B 6Y 2(Fe28) wedge sample corrosion comparison diagram.
Embodiment
The Fe-based amorphous alloy of embodiment one, this embodiment is made up of Fe, Co, Cr, Mo, C, B, Y; With purity is that 99.7% to 99.9% Fe, Co, Cr, Mo, C, B, Y are according to needed atom proportioning arc melting in the argon gas of titanium absorption; Make it to mix, inhale the tabular non-crystaline amorphous metal Fe that the casting cooling obtains the thick 13mm width of 2mm 24Co 24Cr 15Mo 14C 15B 6Y 2X-ray diffractogram turns out to be complete non-crystalline state.Can obtain its glass transformation temperature (T from the DSC curve g=842K) initial crystallization temperature T x=904K and fusing point T m=1371K.Supercooling liquid phase region is △ T x=62K explains that its amorphous formation ability is fine.Vicker hardness reaches 1298Hv, and the compressed rupture strength of this alloy is 3200Mpa.
Embodiment two, technical scheme are with embodiment one unanimity, and the iron-base block amorphous alloy composition of preparation is Fe 28Co 20Cr 15Mo 14C 15B 6Y 2The Fe of this embodiment 28Co 20Cr 15Mo 14C 15B 6Y 2Non-crystaline amorphous metal has high glass forming ability, and the characteristics of this alloy are that glass transformation temperature is T g=860K, crystallization temperature are T x=900K, its fusing point are T m=1366K, supercooling liquid phase region are that 40K, its amorphous formation ability are better than implementing 1 prepared bulk amorphous alloys.Vicker hardness reaches 1280Hv, and the compressed rupture strength of this alloy is 2800MPa.
Embodiment three, technical scheme such as embodiment one, the large block amorphous composition of preparing is Fe 32Co 16Cr 15Mo 14C 15B 6Y 2, this alloy is a Part of Co of implementing 1 scheme with the Fe replacement, obtains Fe 32Co 16Cr 15Mo 14C 15B 6Y 2Non-crystaline amorphous metal has high glass forming ability, and this alloy is owing to adopt comparatively cheap iron to replace comparatively expensive metal Co, thus reduced cost, and also this alloy has good thermostability.The glass transition temp T of this alloy gBe 854K, crystallization temperature T xFor 893K, fusing point Tm are 1358K, the supercooling liquid phase region width of alloy is 39K, and Vickers' hardness is 1269Hv, and compressed rupture strength is 2750Mpa.
In the implementation process, prepared material uses following formula to represent: Fe 24+xCo 24-xCr 15Mo 14C 15B 6Y 2(0≤x≤10), its thermodynamical coordinate data are documented in table 1; Rate of cooling of the present invention is lower.Composition Fe particularly 28Co 20Cr 15Mo 14C 15B 6Y 2Amorphous formation ability is greater than Fe 41Co 7Cr 15Mo 14C 15B 6Y 2,Because of the wedge sample alloy that under identical condition, prepares, pattern is seen accompanying drawing 4 after the corrosion under identical condition, can know Fe 28Co 20Cr 15Mo 14C 15B 6Y 2Glass forming ability is greater than Fe 41Co 7Cr 15Mo 14C 15B 6Y 2Composition.
The present invention compares with existing Fe-based amorphous alloy has following characteristics: (1) adopts vacuum water-cooled copper mold casting to prepare bulk amorphous alloy; Purity is not less than 99.7% Fe, Co, Cr, Mo, C, B, Y in the argon gas atmosphere of titanium absorption, uses arc melting according to needed atom proportioning; About melting four times; Make it to mix, at last alloy is injected water cooled copper mould, obtain required alloy.The starting material of wanting required for the present invention are technical purity, and preparation technology is simple simultaneously, thereby has reduced cost, and the application potential of industrialization is very big; (2) amorphous phase in the non-crystaline amorphous metal can be verified confirmation through a lot of methods.The X-ray diffractogram of non-crystaline amorphous metal has shown the scattering peak of a wide disperse fully.Fig. 1 is the X-ray diffractogram of the part non-crystaline amorphous metal of listed invention, as can be seen from the figure, any crystallization peak do not occur at the effective resolution of X-ray diffractometer, proves that prepared alloy is a non-crystaline amorphous metal.Non-crystaline amorphous metal provided by the invention all at 1～100K/s, and has very wide supercooling liquid phase region in the critical cooling velocity that does not have under the crystalline situation them, shows that they all have good amorphous formation ability.The glass transition temp Tg of alloying constituent is that 1354～1371 K, liquidus temperature Tl scope are at 1400～1410 K at 828～863 K, crystallization starting temperature Tx in 893～910 K, fusing point Tm scope.The supercooling liquid phase region scope is at 39～73 K.Bigger supercooling liquid phase region generally has good amorphous formation ability; (3) alloy of the present invention has high glass forming ability, the Fe for preparing under the same conditions 28Co 20Cr 15Mo 14C 15B 6Y 2With Fe-based amorphous alloy Fe 41Co 7Cr 15Mo 14C 15B 6Y 2Compare Fe 28Co 20Cr 15Mo 14C 15B 6Y 2Have stronger glass forming ability, can reach 20mm according to accompanying drawing 3 its maximum diameters of prediction; (4) non-crystaline amorphous metal provided by the invention has HS, high firmness, and its compressed rupture strength is at 2700～3600MPa, Vickers' hardness 1270～1310Hv.These performances are higher than other centimetre-sized block amorphous alloy.
Figure 2012103045768100002DEST_PATH_IMAGE001

Claims (5)

1. the Fe-based amorphous alloy material of a high glass forming ability; It is characterized in that it is elementary composition by Fe, Cr, Mo, C, B, Y and Co, press following atom number proportioning: Fe 24 ~ 32%, Co 16 ~ 24%, Cr 15%, Mo 14%, C 15%, B 6%, Y 2%.
2. the Fe-based amorphous alloy material of a kind of high glass forming ability as claimed in claim 1 is characterized in that said Fe, Cr, Mo, C, B, Y and Co element by atom number ratio are: Fe 24%, Co 24%, Cr 15%, Mo 14%, C 15%, B 6%, Y 2%.
3. the Fe-based amorphous alloy material of a kind of high glass forming ability as claimed in claim 1 is characterized in that said Fe, Cr, Mo, C, B, Y and Co element by atom number ratio are: Fe 28%, Co20%, Cr 15%, Mo 14%, C 15%, B 6%, Y 2%.
4. the Fe-based amorphous alloy material of a kind of high glass forming ability as claimed in claim 1 is characterized in that said Fe, Cr, Mo, C, B, Y and Co element by atom number ratio are: Fe 32%, Co16%, Cr 15%, Mo 14%, C 15%, B 6%, Y 2%.
5. like the Fe-based amorphous alloy material of the arbitrary described a kind of high glass forming ability of claim 1 to 4, the purity that it is characterized in that said Fe, Cr, Mo, C, B, Y and Co is 99.7% to 99.9%.
CN2012103045768A 2012-08-24 2012-08-24 Iron-based amorphous alloy material with high glass-forming capability Pending CN102776452A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014566A (en) * 2012-12-21 2013-04-03 西南大学 Iron-based block metal glass with good corrosion resistance and fabrication method of iron-based block metal glass
CN107009048A (en) * 2017-04-24 2017-08-04 南昌航空大学 A kind of Fe-based amorphous welding material of Twin wire arc built-up welding
CN107442778A (en) * 2017-08-02 2017-12-08 鑫精合激光科技发展（北京）有限公司 A kind of 3D printing Fe base amorphous powders and preparation method thereof
CN107470641A (en) * 2017-08-02 2017-12-15 江西省电力设备总厂 A kind of iron-based amorphous powder and preparation method thereof
CN110093570A (en) * 2019-04-16 2019-08-06 东南大学 A kind of Centimeter Level high-strength iron base block amorphous alloy and new copper mold casting method
CN110788326A (en) * 2019-12-02 2020-02-14 南昌航空大学 Method for preparing porous Fe-based amorphous alloy-Al-based composite material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0310052A (en) * 1990-01-16 1991-01-17 Nippon Yakin Kogyo Co Ltd High permeability amorphous alloy having high corrosion resistance, high strength, and high wear resistance and improvement of magnetic property of same
CN1603445A (en) * 2004-11-04 2005-04-06 哈尔滨工业大学 Iron-base bulk amorphous alloy with high glass-forming ability
CN101323951A (en) * 2007-06-13 2008-12-17 中国科学院金属研究所 Preparation of non-magnetic high corrosion resistant amorphous steel coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0310052A (en) * 1990-01-16 1991-01-17 Nippon Yakin Kogyo Co Ltd High permeability amorphous alloy having high corrosion resistance, high strength, and high wear resistance and improvement of magnetic property of same
CN1603445A (en) * 2004-11-04 2005-04-06 哈尔滨工业大学 Iron-base bulk amorphous alloy with high glass-forming ability
CN101323951A (en) * 2007-06-13 2008-12-17 中国科学院金属研究所 Preparation of non-magnetic high corrosion resistant amorphous steel coating

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014566A (en) * 2012-12-21 2013-04-03 西南大学 Iron-based block metal glass with good corrosion resistance and fabrication method of iron-based block metal glass
CN107009048A (en) * 2017-04-24 2017-08-04 南昌航空大学 A kind of Fe-based amorphous welding material of Twin wire arc built-up welding
CN107009048B (en) * 2017-04-24 2019-01-25 南昌航空大学 A kind of Fe-based amorphous welding material of Twin wire arc built-up welding
CN107442778A (en) * 2017-08-02 2017-12-08 鑫精合激光科技发展（北京）有限公司 A kind of 3D printing Fe base amorphous powders and preparation method thereof
CN107470641A (en) * 2017-08-02 2017-12-15 江西省电力设备总厂 A kind of iron-based amorphous powder and preparation method thereof
CN107442778B (en) * 2017-08-02 2020-05-01 鑫精合激光科技发展（北京）有限公司 Fe-based amorphous powder for 3D printing and preparation method thereof
CN110093570A (en) * 2019-04-16 2019-08-06 东南大学 A kind of Centimeter Level high-strength iron base block amorphous alloy and new copper mold casting method
CN110788326A (en) * 2019-12-02 2020-02-14 南昌航空大学 Method for preparing porous Fe-based amorphous alloy-Al-based composite material
CN110788326B (en) * 2019-12-02 2021-06-25 南昌航空大学 Method for preparing porous Fe-based amorphous alloy-Al-based composite material

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Application publication date: 20121114