CN114433823A - Oriented ZrCr-based alloy and preparation method thereof - Google Patents

Oriented ZrCr-based alloy and preparation method thereof Download PDF

Info

Publication number
CN114433823A
CN114433823A CN202210061767.XA CN202210061767A CN114433823A CN 114433823 A CN114433823 A CN 114433823A CN 202210061767 A CN202210061767 A CN 202210061767A CN 114433823 A CN114433823 A CN 114433823A
Authority
CN
China
Prior art keywords
zrcr
alloy
based alloy
directional
oriented
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
CN202210061767.XA
Other languages
Chinese (zh)
Other versions
CN114433823B (en
Inventor
陈�光
黄腾达
郑功
彭海鑫
金志�
周冰
逯帆
凌碧波
刘旭
雷明
侯锐
李啸海
陆春华
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.)
Nanjing University of Science and Technology
Original Assignee
Nanjing University of Science and Technology
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 Nanjing University of Science and Technology filed Critical Nanjing University of Science and Technology
Priority to CN202210061767.XA priority Critical patent/CN114433823B/en
Publication of CN114433823A publication Critical patent/CN114433823A/en
Application granted granted Critical
Publication of CN114433823B publication Critical patent/CN114433823B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B22D27/045—Directionally solidified castings
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a directional ZrCr based alloy and a preparation method thereof, wherein the ZrCr based alloy is marked as Zr according to atomic percent85Cr15The structure is directional dendrite; the method comprises the following steps: selecting proper components according to a ZrCr binary alloy system phase diagram; preparing a cylindrical rod master alloy by adopting a water-cooled copper crucible and a vacuum non-consumable arc melting furnace; and (3) directionally solidifying the master alloy rod by adopting a Bridgman crystal growth device to obtain the ZrCr-based alloy with the directional dendritic crystal structure. Compared with the ZrCr based alloy of isometric crystal, the oriented ZrCr based alloy prepared by the invention has more excellent comprehensive mechanical property.

Description

Oriented ZrCr-based alloy and preparation method thereof
Technical Field
The invention belongs to the technical field of whole-process directional solidification, and particularly relates to a directional ZrCr-based alloy and a preparation method thereof.
Background
With the development of aerospace science and technology and the continuous promotion of space exploration tasks, China continuously develops a series of aerospace activities such as space station construction, deep space exploration and the construction of novel space infrastructures. Therefore, the spacecraft is confronted with the examination of a new task, a new orbit and a new environment, in particular to the examination of the structure and the functional materials of the spacecraft by the severe radiation environment.
The Zr alloy has the characteristics of high hardness, high melting point, extremely low thermal neutron absorption area, low expansion coefficient, good radiation resistance, excellent corrosion resistance and the like, and has wide application prospect in the fields of aerospace, nuclear industry and the like. The Cr element is taken as a typical beta phase stabilizing element, can reduce the temperature of beta → alpha phase transition of the alloy, is beneficial to regulating and controlling the microstructure of the alloy, and simultaneously, the corrosion resistance of the alloy can be improved by adding the Cr element. In addition, from the Zr-Cr binary phase diagram, ZrCr generated in the alloy phase transformation process2 Intermetallic compounds belong to the class of Laves phases. The Laves phase has the advantages of high melting point, high strength, low density, high chemical stability, excellent high-temperature oxidation resistance and the like, and can be used as a reinforcing phase to obviously improve the high-temperature mechanical property of a structural material. However, the Laves phase has poor brittle large deformation capability, and easily causes the fracture strength and the elongation of the material to be remarkably reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a directional ZrCr based alloy.
The technical solution for realizing the purpose of the invention is as follows: an oriented ZrCr based alloy with the expression of Zr85Cr15（at.%）。
The preparation method of the oriented ZrCr based alloy comprises the following steps:
(1) weighing raw materials according to the components of the target ZrCr alloy;
(2) smelting and casting to obtain a ZrCr alloy rod;
(3) under the protection of argon, a Bridgman crystal growth device is adopted to carry out directional solidification on the cylindrical rod alloy, the heating temperature is 1600-1900 ℃, the heat preservation time is 1-60 min, and the drawing speed is 0.1-1000 mu m/s, so that the ZrCr-based alloy is obtained.
Preferably, in the step (2), a water-cooled copper crucible suspension smelting furnace or a vacuum non-consumable arc smelting furnace is adopted to repeatedly smelt the raw materials for at least 5 times, and then the raw materials are cast by the vacuum non-consumable arc smelting furnace to obtain the ZrCr alloy round bar with the diameter of 8-10 mm.
Preferably, in the step (3), the heating temperature is 1700 to 1800 ℃, the heat preservation time is 30 to 60min, and the drawing speed is 25 to 100 μm/s.
Preferably, in the step (3), the ZrCr based alloy with the diameter of 8-10 mm and the length of 6-8 cm is obtained through directional solidification.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the ZrCr alloy prepared by the method has a directional dendritic crystal structure, and controls alpha-ZrCr2 The Laves phase is separated out in a eutectoid lamellar layer, so that the embrittlement behavior of the Laves phase is improved, and the comprehensive mechanical property of the ZrCr alloy is improved.
(2) The method utilizes the unique characteristics of the Bridgman directional solidification device to prepare the ZrCr alloy with the directional dendritic crystal structure in one step, and has simple preparation method and lower process cost.
Drawings
FIG. 1 is a phase diagram of a binary system of ZrCr alloy.
FIG. 2 is a scanning microstructure of a directionally solidified ZrCr alloy of example 1 (a is a scanning image, and b is a surface scanning image of a).
FIG. 3 is a table of the dot scan results and compositions of the directionally solidified ZrCr alloy of example 1.
FIG. 4 is a macroscopic view and an optical microscopic view (a is the as-cast region, b is the competition region, c is the stable region, and d, e are the structures of the enlarged regions in c) of the directionally solidified ZrCr alloy of example 1.
FIG. 5 is a graph of room temperature compressive stress strain for examples 1-3 and as-cast ZrCr alloys.
FIG. 6 is a graph of room temperature tensile stress strain for examples 1-3 and as-cast ZrCr alloys.
FIG. 7 is a micrograph of a directionally solidified ZrCr alloy of example 2.
FIG. 8 is a micrograph of a directionally solidified ZrCr alloy of example 3.
FIG. 9 is a micrograph of a directionally solidified ZrCr alloy of comparative example 1.
FIG. 10 is a micrograph of a directionally solidified ZrCr alloy of comparative example 2.
FIG. 11 is a micrograph of a directionally solidified ZrCr alloy of comparative example 3.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
According to the invention, a hypoeutectic component is selected according to a ZrCr alloy binary phase diagram for experimental research and regular exploration, because in the aspect of directional solidification technology, a directional eutectic structure has many excellent characteristics: the room temperature strength is superior to that of common cast eutectic alloy; the high-temperature phase has excellent thermal stability; because the phase interface bonding is good, the alloy still has high strength, good fatigue resistance and creep resistance at high temperature close to a eutectic point. However, under equilibrium solidification, only the alloy with the eutectic point composition can obtain the eutectic structure, and the application of the alloy is limited by the single property of the eutectic point composition. Therefore, the invention selects a hypoeutectic component (namely Zr) in the hypoeutectic component range of ZrCr85Cr15(at.%)), the hypoeutectic oriented structure characteristics and preferred orientation of which were studied extensively, with the aim of providing a ZrCr alloy with an oriented dendritic structure.
The invention provides a method for regulating and controlling the liquid-solid phase change and solid-state phase change processes of a ZrCr alloy by using a directional solidification technology, researching the solid-liquid interface morphology and the solidification structure evolution law of the alloy at different drawing rates, obtaining a directional structure with preferred orientation and controlling alpha-ZrCr2 The Laves phase is precipitated in a eutectoid lamellar layer, the embrittlement behavior of the Laves phase is improved, and the comprehensive mechanical property of the ZrCr alloy is improved.
Example 1
(1) According to the phase diagram of the ZrCr alloy binary system shown in figure 1, the proportioning component is Zr85Cr15(at.%) of the alloy.
(2) Repeatedly smelting the raw materials for at least 5 times by using a water-cooled copper crucible suspension smelting furnace, and then casting by using a vacuum non-consumable arc smelting furnace to obtain a ZrCr alloy round rod with the diameter of 10 mm;
(3) under the protection of argon, a Bridgman directional solidification device is adopted to directionally solidify the cylindrical rod master alloy, the heating temperature is 1780 ℃, the heat preservation time is 30min, the drawing speed is 50 mu m/s, and finally the ZrCr directional dendritic crystal structure with the diameter of 10mm and the length of 6cm is obtained.
The point/line/surface scanning is carried out on the selected area of the micro-morphology, and the black tissue which is alpha-ZrCr can be obtained2The phase, gray and white texture, is the α -Zr phase. As analyzed by combining the graphs of FIG. 1, FIG. 2 and FIG. 3, during the solidification process, as the temperature is reduced, the liquid-solid phase transformation firstly occurs to precipitate the cellular beta-Zr primary phase, and then the eutectic transformation L → beta-Zr + alpha-ZrCr occurs to the residual liquid phase at about 1332 DEG C2Generating primary vermicular alpha-ZrCr2Eutectic structure with beta-Zr; along with the continuous reduction of the temperature, secondary alpha-ZrCr is precipitated from the eutectic beta-Zr2Phase, finally β -Zr (BCC) → α -Zr (HCP) + α -ZrCr at about 836 ℃2Three times of formation of alpha-ZrCr from cellular beta-Zr2Lamellar structure with α -Zr. The specific structure is shown in FIG. 4, so that the ZrCr alloy with the oriented dendritic structure can be obtained. As can be seen from fig. 5 and 6, the compressive strength of the ZrCr alloy with oriented dendrite structure is 34.4% higher than that of the as-cast ZrCr alloy, the tensile strength is 7.7% higher than that of the as-cast ZrCr alloy, and the elongation is 113% higher than that of the as-cast ZrCr alloy.
Example 2
Adopts the component Zr85Cr15(at.%) of the alloy, the other steps are the same as in example 1, except that: when the alloy is directionally solidified and the drawing speed is 25 μm/s, the ZrCr alloy with the directional dendritic structure of the embodiment 1 can still be obtained, and the micrograph of the ZrCr alloy is shown in FIG. 7. From fig. 5 and 6, it can be seen that the compressive strength of the ZrCr alloy with oriented dendrite structure is 21.4% higher than that of the as-cast ZrCr alloy, the tensile strength is 8.7% higher than that of the as-cast ZrCr alloy, and the elongation is 82.6% higher than that of the as-cast ZrCr alloy.
Example 3
Adopts the component Zr85Cr15(at.%) of the alloy, the other steps are the same as in example 1, except that: when the alloy is directionally solidified and the drawing speed is 100 μm/s, the ZrCr alloy with the directional dendritic structure of the embodiment 1 can still be obtained, and the micrograph thereof is shown in FIG. 8. From fig. 5 and 6, it can be seen that the compressive strength of the ZrCr alloy with oriented dendrite structure is 32.8% higher than that of the as-cast ZrCr alloy, the tensile strength is 19.7% higher than that of the as-cast ZrCr alloy, and the elongation is 326% higher than that of the as-cast ZrCr alloy.
Comparative example 1
Adopts the component of Zr85Cr15(at.%) of the alloy, the other steps are the same as in example 1, except that: during directional solidification, the drawing speed is 250 mu m/s, and the ZrCr alloy with the stable section and the non-directional dendritic structure is obtained, and a micrograph of the ZrCr alloy is shown in figure 9.
Comparative example 2
Adopts the component Zr85Cr15(at.%) of the alloy, the other steps are the same as in example 1, except that: during directional solidification, the drawing speed is 500 μm/s, and the ZrCr alloy with the stable section and the non-directional dendritic structure is obtained, and a micrograph of the ZrCr alloy is shown in figure 10.
Comparative example 3
Adopts the component of Zr85Cr15(at.%) of the alloy, the other steps are the same as in example 1, except that: when the alloy is directionally solidified, the drawing speed is 1000 mu m/s, and the ZrCr alloy with the stable section and the non-directional dendritic structure is obtained, and a micrograph of the ZrCr alloy is shown as figure 11.

Claims (6)

1. The preparation method of the oriented ZrCr based alloy is characterized in that the expression is Zr85Cr15The method comprises the following steps:
(1) weighing raw materials according to the components of the target ZrCr alloy;
(2) obtaining a ZrCr alloy rod through smelting and casting;
(3) under the protection of argon, a Bridgman crystal growth device is adopted to carry out directional solidification on the cylindrical rod alloy, the heating temperature is 1600-1900 ℃, the heat preservation time is 1-60 min, and the drawing speed is 0.1-1000 mu m/s, so that the ZrCr-based alloy is obtained.
2. The method of claim 1, wherein in step (2), the raw material is repeatedly smelted at least 5 times using a water-cooled copper crucible suspension smelting furnace or a vacuum non-consumable arc smelting furnace.
3. The method according to claim 1, wherein the ZrCr alloy round bar with the diameter of 8-10 mm is obtained by casting through a vacuum non-consumable arc melting furnace.
4. The method according to claim 1, wherein in the step (3), the heating temperature is 1700 to 1800 ℃, the holding time is 30 to 60min, and the drawing speed is 25 to 100 μm/s.
5. The method according to claim 1, wherein in the step (3), the directional solidification is performed to obtain a ZrCr-based alloy having a diameter of 8 to 10mm and a length of 6 to 8 cm.
6. An oriented ZrCr based alloy prepared according to the method of any one of claims 1 to 5.
CN202210061767.XA 2022-01-19 2022-01-19 Oriented ZrCr based alloy and preparation method thereof Active CN114433823B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210061767.XA CN114433823B (en) 2022-01-19 2022-01-19 Oriented ZrCr based alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210061767.XA CN114433823B (en) 2022-01-19 2022-01-19 Oriented ZrCr based alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114433823A true CN114433823A (en) 2022-05-06
CN114433823B CN114433823B (en) 2023-03-31

Family

ID=81368617

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210061767.XA Active CN114433823B (en) 2022-01-19 2022-01-19 Oriented ZrCr based alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114433823B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080071347A1 (en) * 2006-09-15 2008-03-20 Boston Scientific Scimed, Inc. Medical devices having alloy compositions
CN113528926A (en) * 2021-06-11 2021-10-22 南京理工大学 Oriented FeAl-based alloy and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080071347A1 (en) * 2006-09-15 2008-03-20 Boston Scientific Scimed, Inc. Medical devices having alloy compositions
CN113528926A (en) * 2021-06-11 2021-10-22 南京理工大学 Oriented FeAl-based alloy and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
K.S. KUMAR, L. PANG, J.A. HORTON, C.T. LIU: "Structure and composition of Laves phases in binary Cr–Nb,Cr–Zr and ternary Cr–(Nb, Zr) alloys", 《INTERMETALLICS》 *
SUKLYUN HONG, C.L. FU: "Theoretical study on cracking behavior in two-phase alloys Cr–Cr2X (X=Hf, Nb, Ta, Zr)", 《INTERMETALLICS》 *
T. TAKASUGI, K.S. KUMAR, C.T. LIU, E.H. LEE: "Microstructure and mechanical properties of two-phase Cr–Cr2Nb,Cr–Cr2Zr and Cr–Cr2(Nb,Zr) alloys", 《MATERIALS SCIENCE AND ENGINEERING A》 *
郑海忠等: "Laves相NbCr_2室温脆性的研究进展", 《稀有金属材料与工程》 *

Also Published As

Publication number Publication date
CN114433823B (en) 2023-03-31

Similar Documents

Publication Publication Date Title
Jung et al. Microstructure control of TiAl alloys containing β stabilizers by directional solidification
Zhang et al. Recent progress in high-entropy alloys
Pan et al. Microstructural formation in a hypereutectic Mg–Si alloy
Meng et al. Effect of vanadium on the microstructures and mechanical properties of an Al–Mg–Si–Cu–Cr–Ti alloy of 6XXX series
Guo et al. Influence of nano-Y2O3 addition on microstructure and tensile properties of high-Al TiAl alloys
CN105268973A (en) Additive manufacturing method for functional material part based on TiNi memory alloy wire
CN106636746B (en) A kind of high-strength high-elongation ratio high-temperature titanium alloy and its preparation process
CN110643851A (en) TiAl-based composite material and thermal mechanical treatment method thereof
Ramakrishnan et al. Functionally graded metal matrix composite of Haynes 282 and SiC fabricated by laser metal deposition
Wang et al. Improvement of the creep lifetimes and microstructural stability of β-solidifying γ-TiAl by cold crucible directional solidification
CN106435318B (en) A kind of vanadium alloy of high-strength and high ductility and preparation method thereof
Zhang et al. Microstructure and mechanical properties of novel Zr–Al–V alloys processed by hot rolling
Shang et al. Investigations on the solidification microstructures and room temperature compression properties of Nb-doped NiAl-32Cr-6Mo hypereutectic alloy
Şahin et al. Microstructural evolution and mechanical properties of Sn-Bi-Cu ternary eutectic alloy produced by directional solidification
CN114433823B (en) Oriented ZrCr based alloy and preparation method thereof
Fang et al. Effect of cyclic heat treatment on microstructures and mechanical properties of directionally solidified Ti–46Al–6Nb alloy
Li et al. Simultaneously increasing mechanical and corrosion properties in CoCrFeNiCu high entropy alloy via friction stir processing with an improved hemispherical convex tool
Cui et al. Deformation behavior and microstructure of DS NiAl/Cr (Mo) alloy containing Hf
Jiang et al. Grain refinement and excellent mechanical properties of a Ti-based alloy via laser melting and subsequent low temperature annealing
CN113652590B (en) TiHfFeNiNb with high strength and high elastic strain x Directional solidification high-entropy alloy and preparation thereof
Muto et al. Directional Solidification of TiAl‐based Alloys and Properties of Directionally Solidified Ingots
CN113430418B (en) Ce-added Ti6Al4V titanium alloy and preparation method thereof
Zheng et al. Investigation of three-step heat treatments on the microstructure and steady-state creep behaviors of (TiB+ TiC+ Y2O3)/α-Ti composite
Chen et al. Effect of Zr on microstructure and mechanical properties of binary TiAl alloys
Harbur et al. STUDIES ON THE U--Pu--Zr ALLOY SYSTEM FOR FAST BREEDER REACTOR APPLICATIONS.

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Chen Guang

Inventor after: Lei Ming

Inventor after: Hou Rui

Inventor after: Li Xiaohai

Inventor after: Lu Chunhua

Inventor after: Ling Bibo

Inventor after: Zheng Gong

Inventor after: Huang Tengda

Inventor after: Peng Haixin

Inventor after: Jin Zhi

Inventor after: Zhou Bing

Inventor after: Lu Fan

Inventor after: Liu Xu

Inventor before: Chen Guang

Inventor before: Lei Ming

Inventor before: Hou Rui

Inventor before: Li Xiaohai

Inventor before: Lu Chunhua

Inventor before: Huang Tengda

Inventor before: Zheng Gong

Inventor before: Peng Haixin

Inventor before: Jin Zhi

Inventor before: Zhou Bing

Inventor before: Lu Fan

Inventor before: Ling Bibo

Inventor before: Liu Xu

GR01 Patent grant
GR01 Patent grant