CN106222486B - A kind of high intensity zirconium titanium ferro-aluminum vanadium alloy and preparation method thereof - Google Patents

A kind of high intensity zirconium titanium ferro-aluminum vanadium alloy and preparation method thereof Download PDF

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CN106222486B
CN106222486B CN201610878710.3A CN201610878710A CN106222486B CN 106222486 B CN106222486 B CN 106222486B CN 201610878710 A CN201610878710 A CN 201610878710A CN 106222486 B CN106222486 B CN 106222486B
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zirconium
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CN106222486A (en
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张新宇
李俊
秦家千
马明臻
刘日平
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Yanshan University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • C22F1/183High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

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Abstract

A kind of high intensity zirconium titanium ferro-aluminum vanadium alloy, mass percent are as follows:The content of zirconium is 29.5 30.5%, and the content of aluminium is 4.5 5.5%, and the content of vanadium is 2.5 3.5%, and the content of iron is 0.5 2.0%, and surplus is titanium and inevitable impurity.The preparation method of the alloy mainly weighs above-mentioned raw materials according to percentage contents, the certain number of non-consumable vacuum melting furnace melting is put into ensure uniformly, obtain alloy cast ingot, ingot casting is put into Muffle furnace again and is heated to certain temperature, multi-pass is hot-rolled down to the thickness of needs in the same direction, each hot rolled thickness is certain, finally obtains rolling state alloy.The present invention, by the quantitative aluminium of addition, vanadium, ferro element, becomes the addition of titanium alloy, especially ferro element with high intensity, high rigidity, plays the role of crystal grain thinning, improve the intensity of alloy using two kinds of elements of titanium zirconium as alloy bulk.Its yield strength is 1299 1553MPa, and tensile strength is 1420 1667MPa, and Vickers hardness is 436 483HV.

Description

A kind of high intensity zirconium titanium ferro-aluminum vanadium alloy and preparation method thereof
Technical field
The present invention relates to a kind of zirconium titanium-base alloys and preparation method thereof.
Background technology
Zirconium and titanium belong to same main group in element mid-term table, and zircaloy and titanium alloy have many similar characteristics, such as Intensity height, good, the heat-resist, good biocompatibility of corrosion resistance etc..Metal zirconium has small neutron-absorbing area, high corrosion-resistant and height The characteristics such as fusing point (1860 DEG C) so that it is widely used in nuclear industry.Titanium alloy has high specific strength and excellent The characteristics such as high-temperature behavior, obtained important application in mechanical automation and aircraft industry.With zirtan type not Disconnected abundant and development, zirtan is gradually paid close attention to as engineering structure part material, in many aspects especially in aviation Application in aerospace industry field is more and more.But the as-cast structure of zirconium titanium-base alloy is coarse, causes intensity low.
Invention content
The purpose of the present invention is to provide a kind of high intensity zirconium titanium ferro-aluminum vanadium alloys and preparation method thereof.The present invention is mainly Using two kinds of elements of titanium zirconium as alloy bulk, by adding in a certain amount of aluminium, iron, vanadium and carrying out heat treatment, preparation is provided There are the zirconium titanium-base alloy and preparation method of higher-strength.
1st, zirconium titanium ferro-aluminum vanadium alloy of the invention:
High intensity zirconium titanium ferro-aluminum vanadium alloy its chemical composition mass percent of the present invention is:Zirconium content is 29.5- 30.5%, the content of aluminium is 4.5-5.5%, and the content of vanadium is 2.5-3.5%, and the content of iron is 0.5-2.0%, remaining for titanium and Inevitable impurity.
2nd, above-mentioned zirconium titanium ferro-aluminum vanadium alloy preparation method:
(1) it pre-processes:It is polished raw material and uses ultrasonic cleaning, finally dried up with hair-dryer;
(2) ingot casting:Will step (1) raw material mix after be put into vacuum non-consumable smelting furnace, in vacuum degree 2.0 × 10-2Pa meltings at least 8 times, the time of each sample melting is 1-1.5min every time, to ensure to obtain the uniform zirconium titanium aluminium of ingredient Ferrovanadium ingot;
(3) hot rolling:The zirconium titanium ferro-aluminum vanadium alloy ingot that step (2) obtains is put into Muffle furnace and is heated to Muffle furnace 900-1000 DEG C, 30-60min is kept the temperature, then multi- pass rolling deformation will be carried out on alloy pig fast transfer to roll mill;First In above-mentioned temperature 3-5min after the completion of secondary rolling, second of rolling deformation is then quickly carried out, is recycled according to this, pushed every time Amount controls the 9-11% in alloy pig original depth, and alloy pig deflection is finally made to reach 70%;After the deformation of last a time, Sheet alloy is positioned in air and is cooled to room temperature;The sheet alloy surface that will be cooled to room temperature is stripped off the skin and figuring of surface Obtain high intensity zirtan.
The present invention has the following advantages that compared with prior art:
1st, alloy strength is high, hardness is high, yield strength 1299-1553MPa, tensile strength 1420-1667MPa, Vickers hardness is 436-483HV.
2nd, due to adding ferro element in alloy raw material, achieve the purpose that stable β phases, iron is as a kind of cheap β phase stabilisers are introduced into the present invention can improve alloy property, be found by many experiments, and iron has refining alloy crystal grain, Improve the effect of alloy strength.
3rd, preparation method of the present invention is easy, easy to operate.
Description of the drawings
Fig. 1 is 1-4 of embodiment of the present invention molten alloy rolling state X-ray diffractogram.
Fig. 2 is 1 molten alloy hot rolling post-tensioning force diagram figure of the embodiment of the present invention.
Fig. 3 is the transmission plot for not adding ferroalloy.
Fig. 4 is the transmission plot of 1 molten alloy of embodiment of the present invention rolling state.
Fig. 5 is the transmission plot of 2 molten alloy of embodiment of the present invention rolling state.
Fig. 6 is the transmission plot of 3 molten alloy of embodiment of the present invention rolling state.
Explanation:
As can be seen from Figure 1 with the increase of iron content, alloy phase composition is β phases by α phase transition;
The alloy tensile intensity reaches 1420MPa as can be seen from Figure 2, and extensibility reaches 5%;
Wherein lath-shaped crystal belongs to α phases crystal grain (being obtained by the judgement of corresponding SAED data) as can be seen from Figure 3, compared with It is coarse.
Wherein acicular crystal belongs to α phases crystal grain (being obtained by the judgement of corresponding SAED data) as can be seen from Figure 4, relatively schemes α phases crystal grain is narrower in 3, is the raised effect of iron content.
Identical conclusion can be obtained from Fig. 5,6:Ferro element can make α phase crystal grain become smaller, alloy strength higher.
Specific embodiment
Embodiment 1
Technical grade sponge zirconium 23.6g, titanium sponge 49.2g, pure vanadium 2.8g, fine aluminium 4.0g, iron 0.4g are taken, it is true to be placed in non-consumable In empty arc-melting furnace, in vacuum degree 2.0 × 10-2Pa melt backs 9 times, the smelting time of each sample 1.0 minutes, obtain every time To the uniform alloy cast ingot of ingredient.Melted alloy cast ingot in smelting furnace is cooled down and is taken out after ten minutes.By Muffle furnace liter Temperature is put into alloy cast ingot and keeps the temperature 30 minutes, ensure ingot casting whole heat penetration, ingot casting is taken out from Muffle furnace to 1000 DEG C, quick to turn Move to progress multi- pass rolling deformation on two roll surface milling trains;It is placed into Muffle furnace after the completion of rolling for the first time and keeps the temperature 3 minutes, Take out again it is quick carry out second of rolling in the same direction, recycle according to this, each volume under pressure control is the 9% of alloy pig original depth, most After alloy pig deflection is made to reach 70%;After the deformation of last a time, sheet alloy is positioned in air and is cooled to room temperature; The sheet alloy surface that will be cooled to room temperature strips off the skin and obtains high intensity zirtan with figuring of surface.
Alloy after rolling is processed by standard tensile specimen using cutting on line machine, in instron5982 mechanical properties Its tensile mechanical properties is tested on test machine, tensile speed is:0.375mm/min, and measure sample with extensometer all-the-way tracking Length variation in drawing process.Specific experiment data are shown in Table 1.
Embodiment 2
Technical grade sponge zirconium 24.0g, titanium sponge 48.8g, pure vanadium 2.8g, fine aluminium 3.6g, iron 0.8g are taken, it is true to be placed in non-consumable In empty arc-melting furnace, in vacuum degree 2.0 × 10-2Pa melt backs 9 times, the smelting time of each sample 1.5 minutes, obtain every time To the uniform alloy cast ingot of ingredient.Melted alloy cast ingot in smelting furnace is cooled down and is taken out after ten minutes.By Muffle furnace liter Temperature is put into alloy cast ingot and keeps the temperature 40 minutes, ensure ingot casting whole heat penetration, ingot casting, fast transfer are taken out from Muffle furnace to 950 DEG C Multi- pass rolling deformation is carried out on to two roll surface milling trains;It is placed into Muffle furnace after the completion of rolling for the first time and keeps the temperature 4 minutes, taken Go out again it is quick carry out second of rolling in the same direction, recycle according to this, each volume under pressure control is the 10% of alloy pig original depth, finally Alloy pig deflection is made to reach 70%;After the deformation of last a time, sheet alloy is positioned in air and is cooled to room temperature;It will The sheet alloy surface being cooled to room temperature strips off the skin obtains high intensity zirtan with figuring of surface.
Alloy after rolling is processed by standard tensile specimen using cutting on line machine, in instron5982 mechanical properties Its tensile mechanical properties is tested on test machine, tensile speed is:0.375mm/min, and measure sample with extensometer all-the-way tracking Length variation in drawing process.Specific experiment data are shown in Table 1.
Embodiment 3
Technical grade sponge zirconium 24.4g, titanium sponge 48.8g, pure vanadium 2.0g, fine aluminium 4.0g, iron 1.2g are taken, it is true to be placed in non-consumable In empty arc-melting furnace, in vacuum degree 2.0 × 10-2Pa melt backs 9 times, the smelting time of each sample 1.5 minutes, obtain every time To the uniform alloy cast ingot of ingredient.Melted alloy cast ingot in smelting furnace is cooled down and is taken out after ten minutes.By Muffle furnace liter Temperature is put into alloy cast ingot and keeps the temperature 50 minutes, ensure ingot casting whole heat penetration, ingot casting, fast transfer are taken out from Muffle furnace to 900 DEG C Multi- pass rolling deformation is carried out on to two roll surface milling trains;It is placed into Muffle furnace after the completion of rolling for the first time and keeps the temperature 5 minutes, taken Go out again it is quick carry out second of rolling in the same direction, recycle according to this, each volume under pressure control is the 11% of alloy pig original depth, finally Alloy pig deflection is made to reach 70%;After the deformation of last a time, sheet alloy is positioned in air and is cooled to room temperature;It will The sheet alloy surface being cooled to room temperature strips off the skin obtains high intensity zirtan with figuring of surface.
Alloy after rolling is processed by standard tensile specimen using cutting on line machine, in instron5982 mechanical properties Its tensile mechanical properties is tested on test machine, tensile speed is:0.375mm/min, and measure sample with extensometer all-the-way tracking Length variation in drawing process.Specific experiment data are shown in Table 1.
Embodiment 4
Technical grade sponge zirconium 24.0g, titanium sponge 48.0g, pure vanadium 2.0g, fine aluminium 4.4g, iron 1.6g are taken, it is true to be placed in non-consumable In empty arc-melting furnace, in vacuum degree 2.0 × 10-2Pa melt backs 9 times, the smelting time of each sample 1.5 minutes, obtain every time To the uniform alloy cast ingot of ingredient.Melted alloy cast ingot in smelting furnace is cooled down and is taken out after ten minutes.By Muffle furnace liter Temperature is put into alloy cast ingot and keeps the temperature 60 minutes, ensure ingot casting whole heat penetration, ingot casting, fast transfer are taken out from Muffle furnace to 900 DEG C Multi- pass rolling deformation is carried out on to two roll surface milling trains;It is placed into Muffle furnace after the completion of rolling for the first time and keeps the temperature 5 minutes, taken Go out again it is quick carry out second of rolling in the same direction, recycle according to this, each volume under pressure control is the 11% of alloy pig original depth, finally Alloy pig deflection is made to reach 70%;After the deformation of last a time, sheet alloy is positioned in air and is cooled to room temperature;It will The sheet alloy surface being cooled to room temperature strips off the skin obtains high intensity zirtan with figuring of surface.
Alloy after rolling is processed by standard tensile specimen using cutting on line machine, in instron5982 mechanical properties Its tensile mechanical properties is tested on test machine, tensile speed is:0.375mm/min, and measure sample with extensometer all-the-way tracking Length variation in drawing process.Specific experiment data are shown in Table 1.
1 alloy of the present invention of table and prior art alloy mechanical property test comparison table
As can be seen that the yield strength of the present invention is 2-3 times of prior art alloy from figure.

Claims (3)

1. a kind of high intensity zirconium titanium ferro-aluminum vanadium alloy, it is characterised in that:Its mass percent is as follows:The content of zirconium is 29.5- 30.5%, the content of aluminium is 4.5-5.5%, and the content of vanadium is 2.5-3.5%, and the content of iron is 0.5-2.0%, remaining for titanium and Inevitable impurity;
The preparation method of the high intensity zirconium titanium ferro-aluminum vanadium alloy is:
(1) ingot casting:Raw material are put into vacuum non-consumable smelting furnace, in vacuum degree 2.0 × 10-2Pa meltings at least 8 times, every time The time of each sample melting is 1-1.5min, obtains the uniform zirconium titanium ferro-aluminum vanadium alloy ingot of ingredient;
(2) hot rolling:Above-mentioned zirconium titanium ferro-aluminum vanadium alloy ingot casting is put into Muffle furnace and Muffle furnace is heated to 900-1000 DEG C, is protected Warm 30-60min then will carry out multi- pass rolling deformation on alloy pig fast transfer to roll mill;After the completion of rolling for the first time In above-mentioned temperature 3-5min, second of rolling deformation is then quickly carried out, is recycled according to this, each volume under pressure control is in alloy The 9-11% of ingot original depth finally makes alloy pig deflection reach 70%;After the deformation of last a time, sheet alloy is put It is placed in air and is cooled to room temperature;The sheet alloy surface that will be cooled to room temperature strips off the skin and obtains high intensity zirconium with figuring of surface Titanium ferro-aluminum vanadium alloy.
2. the preparation method of high intensity zirconium titanium ferro-aluminum vanadium alloy described in claim 1, it is characterised in that:
(1) ingot casting:Raw material described in claim 1 are put into vacuum non-consumable smelting furnace, in vacuum degree 2.0 × 10- 2Pa meltings at least 8 times, the time of each sample melting is 1-1.5min every time, obtains the uniform zirconium titanium ferro-aluminum vanadium alloy of ingredient Ingot;
(2) hot rolling:Above-mentioned zirconium titanium ferro-aluminum vanadium alloy ingot casting is put into Muffle furnace and Muffle furnace is heated to 900-1000 DEG C, is protected Warm 30-60min then will carry out multi- pass rolling deformation on alloy pig fast transfer to roll mill;After the completion of rolling for the first time In above-mentioned temperature 3-5min, second of rolling deformation is then quickly carried out, is recycled according to this, each volume under pressure control is in alloy The 9-11% of ingot original depth finally makes alloy pig deflection reach 70%;After the deformation of last a time, sheet alloy is put It is placed in air and is cooled to room temperature;The sheet alloy surface that will be cooled to room temperature strips off the skin and obtains high intensity zirconium with figuring of surface Titanium ferro-aluminum vanadium alloy.
3. the preparation method of high intensity zirconium titanium ferro-aluminum vanadium alloy according to claim 2, it is characterised in that:Raw material are adding It needs to polish to raw material before entering vacuum non-consumable smelting furnace and uses ultrasonic cleaning, finally dried up with hair-dryer.
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