CN103834844A - V and Mn alloyed beta-phase solidified high Nb-TiAl alloy and preparation method thereof - Google Patents

V and Mn alloyed beta-phase solidified high Nb-TiAl alloy and preparation method thereof Download PDF

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CN103834844A
CN103834844A CN201410090686.8A CN201410090686A CN103834844A CN 103834844 A CN103834844 A CN 103834844A CN 201410090686 A CN201410090686 A CN 201410090686A CN 103834844 A CN103834844 A CN 103834844A
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alloy
molar content
melt
tial alloy
alloying
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CN103834844B (en
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陈子勇
宫子琪
周峰
柴丽华
相志磊
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Beijing University of Technology
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Abstract

The invention discloses V and Mn alloyed beta-phase solidified high Nb-TiAl alloy and a preparation method thereof, and belongs to the technical field of alloys. The alloy consists of the following elements in percentage by mole: 43-45% of Al, 5-15% of Nb, V being no higher than 0.5%, Mn being no higher than 1.0%, and the balance of Ti and inevitable impurities. The preparation method comprises the steps of briquetting raw materials according to the composition, meanwhile placing sponge titanium on the edge of inner side of a mold, and then placing a high-purity aluminum layer, an aluminum-niobium intermediate alloy layer, an electrolytic manganese flake layer, an aluminum-vanadium intermediate alloy layer and a sponge titanium layer from bottom to top in a layered mode; placing briquette in a water-cooling copper crucible vacuum induction levitation melting furnace which can be subjected to centrifugal pressure casting, vacuumizing and melting to obtain melt, and uniformly mixing the melt; and casting the melt into a preheated and centrifugal rotating metal cast mold to centrifugally rotate and cast the melt, and cooling the melt along with the furnace. The TiAl alloy disclosed by the invention is uniform and small in structure and free from obvious segregation.

Description

A kind of V, Mn alloying β solidify high Nb-TiAl Alloy And Preparation Method mutually
Technical field
The present invention relates to a kind of high Nb-TiAl alloy and preparation technology thereof, relate in particular to a kind of V, Mn alloying β solidifies high Nb-TiAl Alloy And Preparation Method mutually, belongs to alloy technology field.
Background technology
TiAl alloy is due to advantages such as its low density, low-expansion coefficient, high specific strength, high elastic coefficient and good high temperature and creep resistance antioxidant properties, the lightening fire resistant structured material that is considered to have very much application prospect, can be applicable to the field such as Aeronautics and Astronautics and automobile.But, the drawbacks limit such as the low and hot workability of TiAl Alloy At Room Temperature plasticity is poor its widespread use.Scientific worker by the tissue to TiAl alloy, plasticity and distortion aspect grind in a large number result show, β solidifies mechanical property and the hot workability that can effectively improve TiAl alloy mutually.Along with TiAl alloy is towards temperature high performance high future development, Nb element has become very important a kind of element that adds in TiAl alloy, and it can improve intensity and the high-temperature oxidation resistance of TiAl alloy.Existing research is only the high Nb-TiAl alloy that concentrates on single interpolation β phase stable element, there is not yet report and solidify mutually the preparation of high Nb-TiAl alloy material and polynary β phase stable element V and the physical metallurgy behavior of Mn in high Nb-TiAl alloy about multi-element alloyed β.
Summary of the invention
The object of this invention is to provide and a kind ofly make alloy graining route solidify and be transformed into β and solidify mutually by traditional Peritectic Reaction by add polynary β phase stable element V and Mn in the process of alloy melting, and then the V, the Mn alloying β that improve alloy material structure property solidify high Nb-TiAl alloy material and preparation method thereof mutually.
V of the present invention, Mn alloying β solidify high Nb-TiAl alloy material mutually, it is characterized in that, the molar content of its element is: 43~45% Al, 5~15%(preferably 8%) Nb, not higher than 0.5% V, not higher than the Ti of 1% Mn and surplus and inevitable impurity.
The preparation method that V of the present invention, Mn alloying β solidify high Nb-TiAl alloy mutually, realizes by following step:
(1), take following raw material: titanium sponge, rafifinal, aluminium niobium master alloy, aluminium vanadium master alloy and electrolytic manganese sheet; The Al that the molar content of wherein controlling Al, Nb, V, Mn and Ti element is 43%~45%, 5~15% Nb, not higher than 0.5% V, be not Ti and inevitable impurity higher than 1% Mn and surplus;
(2), step (1) is claimed raw material carry out compound stalk forming by metallic briquette machine, when briquetting, first titanium sponge is placed in to mould surrounding inside edge, the intra-zone then surrounding at titanium sponge from bottom to top each layer be respectively high-purity aluminium lamination, aluminium niobium master alloy layer, aluminium vanadium master alloy layer, electrolytic manganese lamella and sponge titanium layer;
(3) briquetting step (2) being obtained put into can the water jacketed copper crucible vacuum induction suspension smelting furnace of centrifugal casting in, before melting, by metallic mould mould and die preheating to 300~350 ℃, water jacketed copper crucible vacuum induction melting furnace is evacuated to 1.0~3.0 × 10 -3mbar, with the preferred 20kw/min of 20~30kw/min() rate of rise stops increasing power after water jacketed copper crucible vacuum induction melting furnace monitor system is risen to 160~170kw, and then under firm power, melting 200~250s obtains melt, makes melt-mixing even;
(4) melt in step (3) is cast in metallic mould mould in advance preheated and centrifugal rotation, centrifuge speed is preferably 120r/min, and form V, Mn alloying β and solidify mutually high Nb-TiAl alloy cast ingot, and furnace cooling.
In step of the present invention (1), the quality purity of titanium sponge is 99.78%, and the quality purity of rafifinal is 99.99%, and the quality purity of aluminium niobium master alloy is 99.86%, and the quality purity of electrolytic manganese sheet is 99.99%, and the quality purity of aluminium vanadium master alloy is 99.6%; Each raw material is commercially available prod.
The present invention has determined the optimal addn scope of V and Mn, in Material Coagulating Process, V and Mn add the route that solidifies that has changed alloy, by traditional L → L+ β → α → ... become L → L+ β → β → ... the high Nb-TiAl alloy microscopic structure obtaining is very tiny, and without obviously segregation appearance, the β of formation mainly appears at mutually lamella colony grain boundaries and is net distribution.Tiny tissue even, the obvious segregation of nothing is conducive to the hot workability of alloy, improves the over-all properties of alloy.
The present invention obtained even tiny and without obvious segregation TiAl alloy structure, and adopt water jacketed copper crucible vacuum induction suspension smelting furnace melting and carry out centrifugal casting, technological process is simple to operation.
Accompanying drawing explanation
V, the Mn alloying β of Fig. 1 embodiment 1 solidifies the high Nb-TiAl alloy Ti-45Al-8Nb-0.5V-1.0Mn cast alloy figure of optical microstructure mutually;
V, the Mn alloying β of Fig. 2 embodiment 1 solidifies high Nb-TiAl alloy Ti-45Al-8Nb-0.5V-1.0Mn cast alloy X-ray diffraction spectrogram mutually;
V, the Mn alloying β of Fig. 3 embodiment 1 solidifies high Nb-TiAl alloy Ti-45Al-8Nb-0.5V-1.0Mn cast alloy scanning electron microscopy mutually;
V, the Mn alloying β of Fig. 4 embodiment 2 solidifies the high Nb-TiAl alloy Ti-43Al-8Nb-0.1V-0.1Mn cast alloy figure of optical microstructure mutually;
V, the Mn alloying β of Fig. 5 embodiment 2 solidifies high Nb-TiAl alloy Ti-43Al-8Nb-0.1V-0.1Mn cast alloy X-ray diffraction spectrogram mutually;
V, the Mn alloying β of Fig. 6 embodiment 2 solidifies high Nb-TiAl alloy Ti-43Al-8Nb-0.1V-0.1Mn cast alloy scanning electron microscopy mutually;
V, the Mn alloying β of Fig. 7 embodiment 3 solidifies the high Nb-TiAl alloy Ti-44Al-8Nb-0.5V-0.35Mn cast alloy figure of optical microstructure mutually;
V, the Mn alloying β of Fig. 8 embodiment 3 solidifies high Nb-TiAl alloy Ti-44Al-8Nb-0.5V-0.35Mn cast alloy X-ray diffraction spectrogram mutually;
V, the Mn alloying β of Fig. 9 embodiment 3 solidifies high Nb-TiAl alloy Ti-44Al-8Nb-0.5V-0.35Mn cast alloy scanning electron microscopy mutually.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following examples.The capacity of following vacuum induction suspension smelting furnace is 5 kilograms.
Embodiment 1
V, the Mn alloying β of the present embodiment solidifies high Nb-TiAl alloy preparation mutually to be realized by following step: one, take following raw material: titanium sponge, rafifinal, aluminium niobium master alloy, electrolytic manganese sheet and aluminium vanadium master alloy, wherein Ti46at.%, Al45at.%, Nb8at.%, V0.5at.%, Mn1.0at.%; Two, step 1 is claimed raw material carry out compound stalk forming by metallic briquette machine, when briquetting, first titanium sponge is placed in to mould inside edge, high-purity aluminium lamination, aluminium niobium master alloy layer, electrolytic manganese lamella, aluminium vanadium master alloy layer and sponge titanium layer are placed in the intra-zone portion layering from bottom to top then surrounding at titanium sponge; Three, briquetting step 2 being obtained put into can the water jacketed copper crucible vacuum induction suspension smelting furnace of centrifugal casting in, before melting, metallic mould is preheated to 350 ℃, water jacketed copper crucible vacuum induction melting furnace is evacuated to 3.0 × 10 -3mbar; Four, stop increasing power after water jacketed copper crucible vacuum induction melting furnace monitor system being risen to 170kw with 20kw/min rate of rise, then under firm power, melting 220s obtains melt, makes melt-mixing even; Five, melt is cast in metallic mould after preheating and centrifugal rotation, centrifuge speed is preferably 120r/min, and ingot casting is of a size of φ 60 × 180mm, and furnace cooling, obtains Ti-45Al-8Nb-0.5V-1.0Mn alloy cast ingot.
Adopt electric spark wire cutting method to cut 15 × 15 × 10mm sample from ingot casting.Metallographic and scanned sample are ground to 3000 orders through abrasive paper for metallograph from 180 orders, then on polished machine, carry out mechanical polishing, throw afterwards by electropolisher, essence again; X-ray diffraction sample is ground to 1000 orders through washing sand paper from 180 orders, then uses ultrasonic oscillator clean surface; Transmission sample is the thin slice that 0.5mm is thick, is ground to 40um thick with sand paper, then adopts the preparation of two spray thinning technique.Utilize the microstructure of metallography microscope sem observation Ti-45Al-8Nb-0.5V-1.0Mn to find, TiAl alloy be organized as tiny equiaxed grain structure, see Fig. 1; Utilize XRD (X-ray diffractometer) to analyze discovery, in alloy except α 2outside γ phase, also have β to occur mutually, see Fig. 2; Utilize scanning electronic microscope and electronic probe to analyze discovery, white exposes and is mainly distributed in lamella colony grain boundaries and is net distribution, sees Fig. 3.
Embodiment 2
V, the Mn alloying β of the present embodiment solidifies high Nb-TiAl alloy preparation mutually to be realized by following step: one, take following raw material: titanium sponge, rafifinal, aluminium niobium master alloy, electrolytic manganese sheet and aluminium vanadium master alloy, wherein Ti48.8at.%, Al43at.%, Nb8at.%, V0.1at%, Mn0.1at.%; Two, step 1 is claimed raw material carry out compound stalk forming by metallic briquette machine, when briquetting, first titanium sponge is placed in to mould inside edge, high-purity aluminium lamination, aluminium niobium master alloy layer, electrolytic manganese lamella, aluminium vanadium master alloy layer and sponge titanium layer are placed in the intra-zone then surrounding at titanium sponge layering from bottom to top; Three, briquetting step 2 being obtained put into can the water jacketed copper crucible vacuum induction suspension smelting furnace of centrifugal casting in, before melting, by metallic mould mould and die preheating to 310 ℃, water jacketed copper crucible vacuum induction melting furnace is evacuated to 1.2 × 10 -3mbar; Four, stop increasing power after water jacketed copper crucible vacuum induction melting furnace monitor system being risen to 160kw with 20kw/min rate of rise, then under firm power, melting 200s obtains melt, makes melt-mixing even; Five, melt is cast in metallic mould after preheating and centrifugal rotation, centrifuge speed is preferably 120r/min, and ingot casting is of a size of φ 60 × 180mm, and furnace cooling, obtains Ti-43Al-8Nb-0.1V-0.1Mn alloy cast ingot.
Adopt electric spark wire cutting method to cut 15 × 15 × 10mm sample from ingot casting, metallographic and scanned sample are ground to 3000 orders through abrasive paper for metallograph from 180 orders, then throw with electropolisher, is smart; X-ray diffraction sample is ground to 1000 orders through washing sand paper from 180 orders, then to use dehydrated alcohol clean surface, transmission sample be the thin slice that 0.5mm is thick, is ground to 40um thick with sand paper, then adopts the preparation of two spray thinning techniques.Utilize the microstructure of metallography microscope sem observation Ti-43Al-8Nb-0.1V-0.1Mn to find, the tissue of TiAl alloy is tiny equiaxed grain structure, sees Fig. 4; Utilize XRD (X-ray diffractometer) to analyze discovery, in alloy except α 2outside γ phase, also have β to occur mutually, see Fig. 5; Utilize scanning electronic microscope and electronic probe to analyze discovery, white exposes and is mainly distributed in lamella colony grain boundaries and is net distribution, sees Fig. 6.
Embodiment 3
V, the Mn alloying β of the present embodiment solidifies high Nb-TiAl alloy preparation mutually to be realized by following step: one, take following raw material: titanium sponge, rafifinal, aluminium niobium master alloy, electrolytic manganese sheet and aluminium vanadium master alloy, wherein Ti47.15at.%, Al44at.%, Nb8at.%, V0.5at%, Mn0.35at.%; Two, step 1 is claimed raw material carry out compound stalk forming by metallic briquette machine, when briquetting, first titanium sponge is placed in to mould inside edge, high-purity aluminium lamination, aluminium niobium master alloy layer, electrolytic manganese lamella, aluminium vanadium master alloy layer and sponge titanium layer are placed in the intra-zone then surrounding at titanium sponge layering from bottom to top; Three, briquetting step 2 being obtained put into can the water jacketed copper crucible vacuum induction suspension smelting furnace of centrifugal casting in, before melting, by metallic mould mould and die preheating to 330 ℃, water jacketed copper crucible vacuum induction melting furnace is evacuated to 2.4 × 10 -3mbar; Four, stop increasing power after water jacketed copper crucible vacuum induction melting furnace monitor system being risen to 170kw with 20kw/min rate of rise, then under firm power, melting 240s obtains melt, makes melt-mixing even; Five, melt is cast in metallic mould after preheating and centrifugal rotation, centrifuge speed is preferably 120r/min, and ingot casting is of a size of φ 60 × 180mm, and furnace cooling, obtains Ti-44Al-8Nb-0.5V-0.35Mn compound ingot casting.
Adopt electric spark wire cutting method to cut 15 × 15 × 10mm sample from ingot casting, metallographic and scanned sample are ground to 3000 orders through abrasive paper for metallograph from 180 orders, then throw with electropolisher, is smart; X-ray diffraction sample is ground to 1000 orders through washing sand paper from 180 orders, then to use dehydrated alcohol clean surface, transmission sample be the thin slice that 0.5mm is thick, is ground to 40um thick with sand paper, then adopts the preparation of two spray thinning techniques.Utilize the microstructure of metallography microscope sem observation Ti-44Al-8Nb-0.5V-0.35Mn to find, the tissue of TiAl alloy is tiny equiaxed grain structure, sees Fig. 7; Utilize XRD (X-ray diffractometer) to analyze discovery, in alloy except α 2outside γ phase, also have β to occur mutually, see Fig. 8; Utilize scanning electronic microscope and electronic probe to analyze discovery, white exposes and is mainly distributed in lamella colony grain boundaries and is net distribution, sees Fig. 9.
Embodiment 4
(1), take following raw material: titanium sponge, rafifinal, aluminium niobium master alloy, electrolysis chromium sheet and electrolytic manganese sheet; The Al that the molar content of wherein controlling Al, Nb, V, Mn and Ti element is 43%~45%, 8% Nb, 0.1~0.5% V, 0.1~1.0% Mn and Ti and the impurity of surplus;
(2), step (1) is claimed raw material carry out compound stalk forming by metallic briquette machine, when briquetting, first titanium sponge is placed in to mould inside edge, high-purity aluminium lamination, aluminium niobium master alloy layer, electrolytic manganese lamella, aluminium vanadium master alloy layer and sponge titanium layer are placed in the region then surrounding at titanium sponge bottom layering from bottom to top;
(3) briquetting step (2) being obtained put into can the water jacketed copper crucible vacuum induction suspension smelting furnace of centrifugal casting in, before melting, by metallic mould mould and die preheating to 300~350 ℃, water jacketed copper crucible vacuum induction melting furnace is evacuated to 1.0~3.0 × 10 -3mbar, with the preferred 20kw/min of 20~30kw/min() rate of rise stops increasing power after water jacketed copper crucible vacuum induction melting furnace monitor system is risen to 160~170kw, and then under firm power, melting 200~250s obtains melt, makes melt-mixing even;
(4) melt in step (3) is cast in metallic mould mould in advance preheated and centrifugal rotation, centrifuge speed is preferably 120r/min, and form containing V, Mn alloying β and solidify mutually high Nb-TiAl alloy cast ingot, and furnace cooling.
V, the Mn alloying β that adopts the sign identical with embodiment 3 with embodiment 1, embodiment 2 to obtain solidifies the tiny even and obviously segregation of nothing of high Nb-TiAl alloy material microstructure mutually, in tissue, there is the β phase of brilliant white, be mainly distributed in lamella colony grain boundaries and be net distribution.

Claims (8)

1. V, Mn alloying β solidify a high Nb-TiAl alloy mutually, it is characterized in that the molar content of element: 43%~45% Al, 5~15% Nb, not higher than 0.5% V, not higher than the Ti of 1.0% Mn and surplus and inevitable impurity.
2. solidify mutually high Nb-TiAl alloy according to a kind of V of claim 1, Mn alloying β, it is characterized in that, the molar content 8% of Nb, the molar content of V not higher than the molar content of 0.5%, Mn not higher than 1.0%.
3. solidify mutually high Nb-TiAl alloy according to a kind of V of claim 1, Mn alloying β, it is characterized in that, the molar content 8% of Nb, the molar content 0.1-0.5% of V, the molar content of Mn is not higher than 1.0%.
4. solidify mutually high Nb-TiAl alloy according to a kind of V of claim 1, Mn alloying β, it is characterized in that, the molar content 8% of Nb, the molar content 0.1-0.5% of V, the molar content 0.1-1.0% of Mn.
The preparation method that 5.V, Mn alloying β solidify high Nb-TiAl alloy mutually, is characterized in that, comprises the steps:
(1), take following raw material: titanium sponge, rafifinal, aluminium niobium master alloy, electrolytic manganese sheet and aluminium vanadium master alloy; The Al that the molar content of wherein controlling Al, Nb, V, Mn and Ti element is 43%~45%, 5~15% Nb, not higher than 0.5% V, be not Ti and inevitable impurity higher than 1.0% Mn and surplus;
(2), step (1) is claimed raw material carry out compound stalk forming by metallic briquette machine, when briquetting, first titanium sponge is placed in to mould inside edge, high-purity aluminium lamination, aluminium niobium master alloy layer, electrolytic manganese lamella, aluminium vanadium master alloy layer and sponge titanium layer are placed in the intra-zone then surrounding at titanium sponge layering from bottom to top;
(3) briquetting step (2) being obtained put into can the water jacketed copper crucible vacuum induction suspension smelting furnace of centrifugal casting in, before melting, by metallic mould mould and die preheating to 300~350 ℃, water jacketed copper crucible vacuum induction melting furnace is evacuated to 1.0~3.0 × 10 -3mbar, stops increasing power after water jacketed copper crucible vacuum induction melting furnace monitor system being risen to 160~170kw with 20~30kw/min rate of rise, and then under firm power, melting 200~250s obtains melt, makes melt-mixing even;
(4) melt in step (3) is cast in metallic mould mould in advance preheated and centrifugal rotation, forms V, Mn alloying β and solidify mutually high Nb-TiAl alloy cast ingot, and furnace cooling.
6. according to the method for claim 5, it is characterized in that, with 20kw/min rate of rise, water jacketed copper crucible vacuum induction suspension smelting furnace monitor system is risen to 160~170kw and carries out centrifugal casting forming.
7. according to the method for claim 5, it is characterized in that, centrifuge speed is preferably 120r/min.
8. according to the method for claim 5, it is characterized in that, in (1), the quality purity of titanium sponge is 99.78%, the quality purity of rafifinal is 99.99%, the quality purity of aluminium niobium master alloy is 99.86%, and the quality purity of electrolytic manganese sheet is 99.99%, and the quality purity of aluminium vanadium master alloy is 99.6%.
CN201410090686.8A 2014-03-12 2014-03-12 A kind of V, Mn alloying β phase solidifies high Nb containing TiAl based alloy and preparation method thereof Expired - Fee Related CN103834844B (en)

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Cited By (1)

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CN104388714A (en) * 2014-11-03 2015-03-04 中国航空工业集团公司北京航空材料研究院 Smelting preparation method of large-sized titanium-aluminum intermetallic ingot

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* Cited by examiner, † Cited by third party
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