CN102605299B - New technology for preparing metal glass - Google Patents

New technology for preparing metal glass Download PDF

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CN102605299B
CN102605299B CN 201210101573 CN201210101573A CN102605299B CN 102605299 B CN102605299 B CN 102605299B CN 201210101573 CN201210101573 CN 201210101573 CN 201210101573 A CN201210101573 A CN 201210101573A CN 102605299 B CN102605299 B CN 102605299B
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metallic glass
generation
silica tube
metal glass
alloy
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CN102605299A (en
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郭晶
张兆磊
郭晓慧
闫传金
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Shandong Agricultural University
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Shandong Agricultural University
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Abstract

The invention discloses a new technology for preparing metal glass. The new technology for preparing metal glass is introduced by taking the alloys Gd56Al26Co18 and Sm56Al26Co18 as examples, and the method comprises the following steps of: preparing the component in the alloy with the predetermined nominal composition into a master alloy through a vacuum arc melting method; remelting the master alloy by an induction melting method, and preparing the liquid master alloy into the first-generation metal glass by a copper mould blow casting method; polishing and cleaning the first-generation metal glass and putting the polished and cleaned first-generation metal glass into a pretreated quartz tube; heating the first-generation metal glass to a completely molten state by the induction melting method; and molding through copper mould blow casting. The new technology for preparing the metal glass by a twice melting method disclosed by the invention can be used for obviously improving the glass forming capability of alloy, and has the characteristics of simple technology, low cost, broad prospect in the fields of metal glass basic study and application, and the like.

Description

A kind of technology for preparing metallic glass
(1) technical field
The present invention relates to a kind of novel process for preparing metallic glass, belong to material science.
(2) background technology
Metallic glass has excellent mechanics, physics and chemical property such as high strength, high tenacity, high anti-corrosion and high magnetic permeability, and characteristics such as high-accuracy shaping processability.As a kind of novel texture and functional materials, metallic glass begins to be applied in fields such as information and electron device, precision optical machinery, aerospace device and sports movement apparatus, and market outlook are very tempting.How preparing metallic glass is an importance of metallic glass fundamental research, by changing the metallic glass that preparation technology can obtain to have stronger glass forming ability and property, therefore has important use and is worth in addition.
The preparation metallic glass is general both at home and abroad at present adopts the group member with nominal composition at first to be prepared into mother alloy, and then with the mother alloy fusing, utilizes methods such as the casting of vacuum copper mold or quartz tube water quenching to prepare metallic glass.These class methods are just solidified after with mother alloy melting once and are obtained metallic glass, and the size of the metallic glass for preparing is undesirable, and how the glass forming ability that improves alloy by process means is a problem demanding prompt solution.
The constitutional features of metallic glass is to have brachymedial journey ordered structure (being the cluster structure) in unordered, and these microstructures inheritance and development from melt gets, and we can say that melt structure directly influences the formation of metallic glass.Exist the cluster structure that hands down by heredity or influenced by solid-state structure from solid-state in the melt, in process of setting, cluster plays a crucial role to whether obtaining amorphous structure.Whether cluster exists, and how are the kind of cluster and character, all is the factor that influences glass forming ability.Therefore must influence the formation of metallic glass from the solid-state structure that hands down by heredity.
(3) summary of the invention
The present invention has proposed a kind of novel process for preparing metallic glass from solid-state genetic construction angle.
The present invention is prepared into mother alloy by the constituent element that the vacuum arc melting method will be scheduled in the nominal composition alloy; Adopt induction melting with the mother alloy remelting, blow casting by copper mold liquid mother alloy is made first-generation metallic glass; With putting into the silica tube of anticipating after the polishing of first-generation metallic glass, the cleaning, adopt induction melting that first-generation metallic glass is heated to complete melting state more again, blow by copper mold and cast type.
The present invention consists of the following components: the preparation mother alloy, preparation first-generation metallic glass, the amorphous characteristic of detection first-generation metallic glass, preparation s-generation metallic glass, detect the amorphous characteristic of s-generation metallic glass, relatively the glass forming ability of two substituting metal glass.
A kind of novel process for preparing metallic glass, its preparation process is as follows:
1, the atomic percent that will be scheduled in the nominal composition alloy to intend to contain constituent element converts weight percent wt.% to, takes by weighing each constituent element value; With load weighted each constituent element, be placed in the water jacketed copper crucible of arc-melting furnace, adopt the non-consumable arc melting method to carry out melting under the protection of argon gas: melting condition is: at first be evacuated to 10 -3Pa, charging into argon gas to air pressure then is 0.06-0.08MPa, after the fusing, continues to carry out 10 seconds of induction stirring melting again, cooling is then with its upset; Melt back obtains the uniform master alloy ingot of composition more than three times;
2, above-mentioned master alloy ingot is placed in the silica tube, silica tube one end communicates with extraneous argon gas, and an end has the aperture of diameter 2mm, silica tube is put into vacuum blow casting machine, and vacuum is blown the casting machine vacuum chamber and is evacuated to 10 -3Pa, the mode master alloy melting that utilizes ruhmkorff coil to heat, the fusing back is opened and is blown casting device, and outage allows alloy melt charge in the copper mold die cavity by the aperture of silica tube simultaneously, is cooled to room temperature, obtains first-generation metallic glass;
3, will put into silica tube after the polishing of first-generation metallic glass, the cleaning, silica tube one end communicates with extraneous argon gas, and an end has the aperture of diameter 2mm, silica tube is put into vacuum blow casting machine, and vacuum is blown the casting machine vacuum chamber and is evacuated to 10 -3Pa utilizes the mode melting of ruhmkorff coil heating, and the fusing back is opened and blown casting device, and outage allows alloy melt charge in the copper mold die cavity by the aperture of silica tube simultaneously, is cooled to room temperature, obtains s-generation metallic glass.
The amorphous characteristic method of described detection first-generation metallic glass is as follows:
The x-ray diffraction experiment of as cast condition is finished at D/max-rB type X-ray diffractometer.Its sweep limit can reach 5o～100o, and sweep velocity is 4deg/min, and step-length is 0.02o, the Cu target emanation, and operating voltage and electric current are respectively 40kV and 120mA.The X-ray diffraction curve of metallic glass has been usually expressed as a diffuse scattering peak, and crystalline material then shows as the bright and sharp diffraction peak that intensity has nothing in common with each other on the diffraction curve.If have only the peak of a disperse at the X of cast alloy section diffraction curve, show that the alloy that blows casting for the first time is metallic glass.
The amorphous characteristic of described detection s-generation metallic glass is identical with the amorphous characteristic that detects first-generation metallic glass.
The glass forming ability method of described comparison two substituting metal glass is as follows:
The use differential scanning calorimeter detects the thermodynamic characteristics temperature of two substituting metal glass, as: glass transformation temperature T g, crystallization begins temperature T x, fusing point T mAnd liquidus temperature T l, calculate the parameter that characterizes glass forming ability then, as: the reduction glass transformation temperature T Rg= T g/ T lWith γ=T x /( T g + T l) between parameter and supercooling liquid phase region Δ T x =T x- T gUtilize above parameter to compare the glass forming ability of s-generation metallic glass and first-generation metallic glass.Found that s-generation metallic glass has bigger than first-generation metallic glass T Rg, γThe value and Δ T x, show that the glass forming ability of s-generation metallic glass is stronger.
Innovative point of the present invention is:
Innovation on 1 preparation technology.At first prepare first-generation metallic glass, adopt the method for secondary fusion, preparation s-generation metallic glass is through relatively finding, s-generation metallic glass has stronger glass forming ability than first-generation metallic glass, utilizes this technologic innovation can obtain larger sized metallic glass.
2 theoretic innovations.S-generation metallic glass has stronger glass forming ability than first-generation metallic glass, show that the solid-state structure that hands down by heredity from first-generation metallic glass has played promoter action to the formation of s-generation metallic glass, this will form essential understanding to metallic glass important clue will be provided.
Application Areas of the present invention: to the measurement of the first-generation and s-generation metallic glass thermodynamic characteristics temperature, obtain to characterize the parameter of glass forming ability, found that solid-state genetic construction in the first-generation metallic glass can promote the formation of s-generation metallic glass, so the present invention can promote the research of metallic glass basic theory; In application facet, utilize technology of the present invention can improve the glass forming ability of alloy, prepare larger sized metallic glass, to satisfy the needs of structured material.No matter therefore fundamental research or wide prospect is arranged in application facet.
Characteristics such as the novel process of the preparation metallic glass that the present invention proposes can improve the glass forming ability of alloy significantly, and it is simple to have technology, and cost is low.
(4) description of drawings
Fig. 1 is process flow sheet.
1 amorphous characteristic 6 for preparing the amorphous characteristic 4 preparation s-generation metallic glasss 5 detection s-generation metallic glass rods of mother alloy 2 preparation first-generation metallic glasss 3 detection first-generation metallic glasss compares the glass forming ability of two substituting metal glass among Fig. 1
Fig. 2 is the structure iron of vacuum arc melting furnace.
The alloy 11 vacuum arc melting furnace vacuum chambers of 7 cooling tubes, 8 copper crucibles, 9 tungsten electrodes, 10 fusions among Fig. 2
12 furnace walls
Fig. 3 blows casting machine figure for vacuum.
Among Fig. 3 13 expansion links, 14 inlet pipe 15 fixedly test tube screw 16 silica tubes 17 mother alloys 18 copper molds 19 supports 20 ruhmkorff coils 21 vacuum blow the casting machine vacuum chamber
Fig. 4 blows the used silica tube of casting.
22 pipe end aperture 23 quartzy tube walls among Fig. 4
Fig. 5 is Gd 56Al 26Co 18And Sm 56Al 26Co 18The X diffraction curve figure of the first-generation of alloy and s-generation metallic glass rod cross section.
Fig. 6 is the first-generation and s-generation Gd 56Al 26Co 18The DSC curve of metallic glass.
Fig. 7 is the first-generation and s-generation Sm 56Al 26Co 18The DSC curve of metallic glass.
(5) embodiment
With preparation Gd 56Al 26Co 18And Sm 56Al 26Co 18Metallic glass is the specific implementation process that example is narrated this technology.This preparation technology's flow process by the preparation mother alloy, prepares first-generation metallic glass as shown in Figure 1, detect the amorphous characteristic of first-generation metallic glass, preparation s-generation metallic glass, the amorphous characteristic of detection s-generation metallic glass rod, relatively glass forming ability six parts of two substituting metal glass are formed.
Fig. 2 is vacuum arc melting furnace, utilizes this equipment preparation Gd 56Al 26Co 18And Sm 56Al 26Co 18Mother alloy.At first atomic percent is converted into mass percent, Gd 56Al 26Co 18Mass percent be 83.32:6.64:10.04, Sm 56Al 26Co 18Mass percent be 82.70:6.89:10.41; weighing Gd, Al, Co and Sm, Al, Co compound by mass percentage; be placed on respectively in the water jacketed copper crucible 8 of arc-melting furnace, adopt the non-consumable arc melting method under the protection of argon gas, to carry out melting, at first be evacuated to 10 -3Pa, charging into argon gas to air pressure then is 0.06-0.08MPa, after the fusing, continues to carry out 10 seconds of induction stirring melting again, and cooling then with its upset, is carried out melting second time, and melt back like this at least 3 times obtains the uniform Gd of composition respectively 56Al 26Co 18And Sm 56Al 26Co 18Master alloy ingot;
Fig. 3 is that vacuum is blown casting machine figure, and Fig. 4 is silica tube, utilizes copper mold to blow casting and prepares metallic glass.Respectively with an amount of Gd 56Al 26Co 18And Sm 56Al 26Co 18Master alloy ingot places in the silica tube, and silica tube one end communicates with extraneous argon gas, and an end has the aperture of diameter 2mm, silica tube is put into vacuum blow casting machine, and vacuum is blown the casting machine vacuum chamber and is evacuated to 10 -3Pa, the mode master alloy melting that utilizes ruhmkorff coil to heat after the fusing, is opened then and is blown casting device, and outage allows alloy melt charge in the cylindrical, copper model cavity by the aperture of silica tube simultaneously, is cooled to room temperature, obtains the Gd that diameter is 2mm 56Al 26Co 18And Sm 56Al 26Co 18First-generation metallic glass rod.
The x-ray diffraction experiment of as cast condition is finished at D/max-rB type X-ray diffractometer.Its sweep limit can reach 5o～100o, and sweep velocity is 4deg/min, and step-length is 0.02o, the Cu target emanation, and operating voltage and electric current are respectively 40kV and 120mA.The X-ray diffraction curve of metallic glass has been usually expressed as a diffuse scattering peak, and crystalline material then shows as the bright and sharp diffraction peak that intensity has nothing in common with each other on the diffraction curve.At Gd 56Al 26Co 18And Sm 56Al 26Co 18The X diffraction curve of cast alloy section has only the peak of a disperse, shows to blow the Gd of casting for the first time 56Al 26Co 18And Sm 56Al 26Co 18Alloy is metallic glass.
Again respectively with Gd 56Al 26Co 18And Sm 56Al 26Co 18Put into silica tube after the polishing of first-generation metallic glass, the cleaning, silica tube is put into vacuum blow casting machine, vacuum is blown the casting machine vacuum chamber and is evacuated to 10 -3Pa utilizes the mode melting of ruhmkorff coil heating, after the fusing, opens then and blows casting device, and outage allows alloy melt charge in the cylindrical, copper model cavity by the aperture of silica tube simultaneously, is cooled to room temperature, and obtaining diameter is the metallic glass rod of 2mm.
The amorphous characteristic that detects s-generation metallic glass rod is identical with the amorphous characteristic that detects first-generation metallic glass.Fig. 5 is Gd 56Al 26Co 18And Sm 56Al 26Co 18All have only the peak of a disperse on the X diffraction curve figure of the first-generation of alloy and s-generation metallic glass rod cross section, four curves, show that four kinds of alloys all are non-crystalline states.
Fig. 6 and Fig. 7 are the first-generation and s-generation Gd 56Al 26Co 18And Sm 56Al 26Co 18The DSC curve of metallic glass is determined the thermodynamic characteristics temperature of four kinds of metallic glasss according to these four curves, calculates the parameter that characterizes glass forming ability then, and is as shown in table 1.Found that, for Gd 56Al 26Co 18And Sm 56Al 26Co 18Alloy, s-generation metallic glass has bigger than first-generation metallic glass T Rg, γThe value and Δ T x, show that the glass forming ability of s-generation metallic glass is stronger.
Table 1 first-generation and s-generation Gd 56Al 26Co 18And Sm 56Al 26Co 18The parameter of the characteristic temperature of metallic glass and sign glass forming ability
Alloys T g(K) T x(K) T m (K) T l(K) ΔT x T g/ T l γ
Gd 56Al 26Co 18(1) 590 655 951 ? 1059 65 0.557 0.397
Gd 56Al 26Co 18(2) 594 660 951 1059 66 0.561 0.399
Sm 56Al 26Co 18(1) 553 613 864 1000 60 0.553 0.395
Sm 56Al 26Co 18(2) 561 626 863 1003 65 0.559 0.400

Claims (1)

1. technology for preparing metallic glass is characterized in that its preparation process is as follows:
1) converts weight percent wt.% to according to the atomic percent of intending containing constituent element in the predetermined nominal composition alloy, take by weighing each constituent element value; With load weighted each constituent element, be placed in the water jacketed copper crucible of vacuum arc melting furnace, adopt the non-consumable arc melting method to carry out melting under the protection of argon gas: melting condition is: at first be evacuated to 10 -3Pa, charging into argon gas to air pressure then is 0.06-0.08MPa, after the fusing, continues to carry out 10 seconds of induction stirring melting again, cooling is then with its upset; Melt back obtains the even master alloy ingot of composition more than three times;
2) above-mentioned master alloy ingot is placed in the silica tube, silica tube one end communicates with argon gas, and an end has the aperture of diameter 2mm, silica tube is put into vacuum blow casting machine, and vacuum is blown the casting machine vacuum chamber and is evacuated to 10 -3Pa, the mode master alloy melting that utilizes ruhmkorff coil to heat, the fusing back is opened and is blown casting device, and outage allows alloy melt charge in the copper mold die cavity by the aperture of silica tube simultaneously, is cooled to room temperature, obtains first-generation metallic glass;
3) will put into silica tube after the polishing of first-generation metallic glass, the cleaning, silica tube one end communicates with argon gas, and an end has the aperture of diameter 2mm, silica tube is put into vacuum blow casting machine, and vacuum is blown the casting machine vacuum chamber and is evacuated to 10 -3Pa utilizes the mode melting of ruhmkorff coil heating, and the fusing back is opened and blown casting device, and outage allows alloy melt charge in the copper mold die cavity by the aperture of silica tube simultaneously, is cooled to room temperature, obtains s-generation metallic glass.
CN 201210101573 2012-04-09 2012-04-09 New technology for preparing metal glass Expired - Fee Related CN102605299B (en)

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