CN106119651B - A kind of Nb Hf Zr TiO2Alloy bar material and preparation method thereof - Google Patents

A kind of Nb Hf Zr TiO2Alloy bar material and preparation method thereof Download PDF

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CN106119651B
CN106119651B CN201610594561.8A CN201610594561A CN106119651B CN 106119651 B CN106119651 B CN 106119651B CN 201610594561 A CN201610594561 A CN 201610594561A CN 106119651 B CN106119651 B CN 106119651B
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tio
powder
bar material
alloy bar
housing
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CN106119651A (en
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喻吉良
郑欣
刘辉
王峰
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Northwest Institute for Non Ferrous Metal Research
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Northwest Institute for Non Ferrous Metal Research
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof

Abstract

The invention provides a kind of Nb Hf Zr TiO2Alloy bar material, is made up of the raw material of following mass percent：Hf 2%~8%, Zr 3%~7%, TiO24%~10%, surplus is Nb.Present invention also offers a kind of method for preparing the alloy bar material, comprise the following steps：First, by Nb, Hf, Zr and TiO2It is placed in ball mill, ball milling mixing is uniform under argon gas atmosphere protection, obtains mixed-powder；2nd, it is compressing, obtain blank；3rd, blank is fitted into housing, sealed after being vacuumized housing；4th, HIP sintering, obtains Nb Hf Zr TiO2Alloy sintered compact；5th, hot extrusion, obtains Nb Hf Zr TiO2Alloy bar material.Alloy bar material of the present invention has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and elevated temperature strength, the engine component that can be used in aero-turbine.

Description

A kind of Nb-Hf-Zr-TiO2Alloy bar material and preparation method thereof
Technical field
The invention belongs to alloy bar material technical field, and in particular to a kind of Nb-Hf-Zr-TiO2Alloy bar material and its preparation Method
Background technology
Niobium alloy is in 1950s just once as the candidate material of Aero-Space, nuclear engineering and aircraft engine It is widely studied.Although niobium alloy in temperature-room type plasticity, shape very tempting in terms of performance, density and fusing point, it is poor Fatigue strength turn into its major obstacle for being applied as high-temperature structural material.Meanwhile, when temperature in use is more than 1100 DEG C, niobium The creep-resistant property of alloy is remarkably decreased.Alloying element (Mo, Ta, V, W, Hf, Zr, Ti etc.) is added in niobium, alloy can be formed The high niobium alloy of concentration, its mechanical behavior under high temperature is significantly improved, and processing characteristics is good, therefore as high-temperature structural material.Though So by alloying niobic alloy high temperature mechanical property and fatigue strength can be made to obtain a certain degree of improvement, but greatly improve Its mechanical property makes the limited promise that it is applied on high thrust-weight ratio engine of future generation.Therefore, it is necessary to pass through the second phase Dispersion-strengtherning overcomes the shortcoming of single-phase niobium alloy, and design one kind increases ceramic phase in multiphase niobium alloy, and pass through alloying And technology controlling and process, make ceramic phase fine particle even dispersion on niobium matrix, so that its room-temperature mechanical property, high-temperature mechanics It can be significantly improved with fatigue strength, while the temperature-room type plasticity of alloy is not substantially reduced.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of Nb-Hf- for above-mentioned the deficiencies in the prior art Zr-TiO2Alloy bar material.The room temperature tensile intensity of the alloy bar material be 890MPa~987MPa, room temperature elongation percentage be 21%~ 32%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 405MPa~463MPa, and 1300 DEG C of tensile strength is 305MPa~389MPa, thus proves the Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, Excellent fatigue strength and Testing Tensile Strength at Elevated Temperature, the engine component that can be used in aero-turbine.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of Nb-Hf-Zr-TiO2Alloy bar material, Characterized in that, being made up of the raw material of following mass percent：Hf 2%~8%, Zr 3%~7%, TiO24%~10%, Surplus is Nb.
Above-mentioned Nb-Hf-Zr-TiO2Alloy bar material, it is characterised in that be made up of the raw material of following mass percent：Hf 3%~7%, Zr 4%~6%, TiO25%~9%, surplus is Nb.
Above-mentioned Nb-Hf-Zr-TiO2Alloy bar material, it is characterised in that be made up of the composition of following weight percentage： Hf 5%, Zr 5%, TiO27%, surplus is Nb.
Above-mentioned Nb-Hf-Zr-TiO2Alloy bar material, it is characterised in that described Hf, Zr, TiO2It is powder raw material with Nb, The wherein granularity of hafnium powder and zirconium powder is no more than 10 μm, and the granularity of titanium dioxide powder is not more than 5 μm, and the granularity of niobium powder is not more than 20μm。
Above-mentioned Nb-Hf-Zr-TiO2Alloy bar material, it is characterised in that the hafnium powder, zirconium powder and titanium dioxide powder Quality purity is not less than 99.5%, and the quality purity of the niobium powder is not less than 99.9%.
In addition, preparing above-mentioned Nb-Hf-Zr-TiO present invention also offers a kind of2The method of alloy bar material, its feature exists In this method comprises the following steps：
Step 1: by Nb, Hf, Zr and TiO2It is placed in ball mill, ball milling mixing is uniform under argon gas atmosphere protection, obtains Mixed-powder；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, after after the air in housing to be evacuated Seal casinghousing；
Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, temperature be 1500 DEG C~ 1600 DEG C, pressure is HIP sintering 1h~2h under conditions of 150MPa~200MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy sintered compact；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1000 DEG C~1200 in extrusion temperature DEG C, extrusion ratio is to be extruded under conditions of 6~10, and progress strips off the skin processing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy Bar.
Above-mentioned method, it is characterised in that the rotational speed of ball-mill of ball mill described in step one is 200r/min~300r/ Min, the time of the ball milling of the ball mill is 10h~20h.
Above-mentioned method, it is characterised in that housing described in step 3 is hollow cylindrical structure, the material of the housing For pure titanium.
Above-mentioned method, it is characterised in that extrusion temperature described in step 5 is 1050 DEG C~1150 DEG C, and extrusion ratio is 7 ~9.
The present invention has advantages below compared with prior art：
1st, Hf elements and Zr elements are added to Nb-Hf-Zr-TiO by the present invention2In alloy, due to Hf elements and Zr elements There is very high affinity with oxygen, carbon, therefore Hf elements and Zr elements will reduce the oxygen content of Nb matrixes, reduce oxygen element pairing The adverse effect of gold, so as to improve Nb-Hf-Zr-TiO2The temperature-room type plasticity of alloy bar material.
2nd, the present invention is directed to the deficiency of existing niobium alloy bar material, using Hf and Zr solution strengthening, TiO2Second-phase dispersion is strong Change, and Nb-Hf-Zr-TiO is prepared by high temperature insostatic pressing (HIP)+hot extrusion technique process2Alloy bar material, makes small TiO2Ceramic phase Grain even dispersion is distributed on Nb matrixes, so that Nb-Hf-Zr-TiO2Alloy bar material room-temperature mechanical property, mechanical behavior under high temperature It is significantly improved with fatigue strength, while Nb-Hf-Zr-TiO2Alloy bar material temperature-room type plasticity is not substantially reduced.
3rd, the present invention prepares Nb-Hf-Zr-TiO using high temperature insostatic pressing (HIP)+hot extrusion technique process2Alloy bar material, its room temperature resists Tensile strength is that 890MPa~987MPa, room temperature elongation percentage are 21%~32%, through 5 × 106Fatigue after secondary cycling fatigue experiment Intensity is 405MPa~463MPa, and 1300 DEG C of tensile strength is 305MPa~389MPa, the Nb-Hf-Zr-TiO2Alloy bar material With good temperature-room type plasticity and tensile strength, excellent fatigue strength and Testing Tensile Strength at Elevated Temperature can be used in aeroturbine hair Engine component in motivation.
Technical scheme is described in further detail below by drawings and examples.
Brief description of the drawings
Fig. 1 is Nb-Hf-Zr-TiO prepared by the embodiment of the present invention 12The micro-organization chart of alloy bar material.
Embodiment
Embodiment 1
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 5%, Zr 5%, TiO27%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill, the ball under argon gas atmosphere protection Mill is well mixed, obtains mixed-powder；The rotational speed of ball-mill of the ball mill is 250r/min, the time of the ball milling of the ball mill For 15h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, niobium powder Granularity is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the niobium powder Quality purity is not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1550 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 1.5h under conditions of 175MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy burns Knot body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1100 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 8, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO prepared by the embodiment of the present invention 12The microscopic structure of alloy bar material is as shown in Figure 1.Can be with from Fig. 1 Find out, Nb-Hf-Zr-TiO manufactured in the present embodiment2The defects such as cavity, micro-crack are not observed in alloy bar material microstructure, Material is almost completely fine and close.This is due to Nb-Hf-Zr-TiO2Alloy bar material uses high temperature insostatic pressing (HIP)+hot extrusion in preparation process Pressure technical process not only eliminates the defect produced in material preparation process, and crystal grain is reset in hot extrusion process, Make tiny TiO2Ceramic particle is evenly distributed in Nb matrixes, tiny TiO2Ceramic phase particles are to Nb matrix grains and crystal boundary Strong reinforcing is produced, therefore, Nb-Hf-Zr-TiO is greatly improved2Room-temperature mechanical property, the high-temperature mechanics of alloy bar material Energy and fatigue strength.Further, since Hf elements and Zr element solid solutions are in Nb, solution strengthening not only is produced to Nb, it is prior It is due to that Hf elements and Zr elements are reduced with oxygen element, carbon with very high affinity, thus Hf elements and Zr elements Oxygen, carbon content in Nb matrixes, reduce oxygen element, carbon to Nb-Hf-Zr-TiO2The influence of Alloy At Room Temperature plasticity, so as to carry High Nb-Hf-Zr-TiO2The temperature-room type plasticity of alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2The room temperature tensile intensity of alloy bar material is 987MPa, room temperature elongation percentage For 32%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 463MPa, and 1300 DEG C of tensile strength is 389MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and elevated temperature tensile is strong Degree, the engine component that can be used in aero-turbine.
Embodiment 2
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 2%, Zr 3%, TiO24%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill into the ball milling in argon atmosphere It is well mixed, obtain mixed-powder；The rotational speed of ball-mill of the ball mill is 200r/min, and the time of the ball milling of the ball mill is 10h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, the grain of niobium powder Degree is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the matter of the niobium powder Measure purity and be not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1500 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 1h under conditions of 150MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy sintering Body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1000 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 6, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2Alloy bar material room temperature tensile intensity is that 890MPa, room temperature elongation percentage are 21%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 405MPa, and 1300 DEG C of tensile strength is 305MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and high temperature it is strong Degree, the engine component that can be used in aero-turbine.
Embodiment 3
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 8%, Zr 7%, TiO210%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill, the ball under argon gas atmosphere protection Mill is well mixed, obtains mixed-powder；The rotational speed of ball-mill of the ball mill is 300r/min, the time of the ball milling of the ball mill For 20h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, niobium powder Granularity is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the niobium powder Quality purity is not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1600 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 2h under conditions of 200MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy burns Knot body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1200 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 10, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2Alloy bar material room temperature tensile intensity is that 955MPa, room temperature elongation percentage are 26%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 469MPa, and 1300 DEG C of tensile strength is 356MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and high temperature it is strong Degree, the engine component that can be used in aero-turbine.
Embodiment 4
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 3%, Zr 4%, TiO25%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill, the ball under argon gas atmosphere protection Mill is well mixed, obtains mixed-powder；The rotational speed of ball-mill of the ball mill is 220r/min, the time of the ball milling of the ball mill For 13h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, niobium powder Granularity is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the niobium powder Quality purity is not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1550 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 2h under conditions of 200MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy sintering Body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1100 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 8, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2Alloy bar material room temperature tensile intensity is that 932MPa, room temperature elongation percentage are 25%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 417MPa, and 1300 DEG C of tensile strength is 365MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and high temperature it is strong Degree, the engine component that can be used in aero-turbine.
Embodiment 5
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 7%, Zr 6%, TiO29%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill, the ball under argon gas atmosphere protection Mill is well mixed, obtains mixed-powder；The rotational speed of ball-mill of the ball mill is 280r/min, the time of the ball milling of the ball mill For 18h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, niobium powder Granularity is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the niobium powder Quality purity is not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1600 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 1.5h under conditions of 175MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy burns Knot body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1000 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 6, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2Alloy bar material room temperature tensile intensity is that 938MPa, room temperature elongation percentage are 29%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 433MPa, and 1300 DEG C of tensile strength is 338MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and high temperature it is strong Degree, the engine component that can be used in aero-turbine.
Embodiment 6
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 3%, Zr 4%, TiO29%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill, the ball under argon gas atmosphere protection Mill is well mixed, obtains mixed-powder；The rotational speed of ball-mill of the ball mill is 300r/min, the time of the ball milling of the ball mill For 20h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, niobium powder Granularity is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the niobium powder Quality purity is not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1500 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 1h under conditions of 150MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy sintering Body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1150 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 7, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2Alloy bar material room temperature tensile intensity is that 956MPa, room temperature elongation percentage are 30%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 451MPa, and 1300 DEG C of tensile strength is 372MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and high temperature it is strong Degree, the engine component that can be used in aero-turbine.
Embodiment 7
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 7%, Zr 6%, TiO25%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill, the ball under argon gas atmosphere protection Mill is well mixed, obtains mixed-powder；The rotational speed of ball-mill of the ball mill is 220r/min, the time of the ball milling of the ball mill For 15h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, niobium powder Granularity is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the niobium powder Quality purity is not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1600 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 2h under conditions of 200MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy sintering Body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1050 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 7, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2Alloy bar material room temperature tensile intensity is that 961MPa, room temperature elongation percentage are 28%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 452MPa, and 1300 DEG C of tensile strength is 372MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and high temperature it is strong Degree, the engine component that can be used in aero-turbine.
Embodiment 8
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 2%, Zr 3%, TiO210%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill, the ball under argon gas atmosphere protection Mill is well mixed, obtains mixed-powder；The rotational speed of ball-mill of the ball mill is 250r/min, the time of the ball milling of the ball mill For 15h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, niobium powder Granularity is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the niobium powder Quality purity is not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1500 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 1h under conditions of 150MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy sintering Body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1150 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 9, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2Alloy bar material room temperature tensile intensity is that 961MPa, room temperature elongation percentage are 27%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 439MPa, and 1300 DEG C of tensile strength is 372MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and high temperature it is strong Degree, the engine component that can be used in aero-turbine.
Embodiment 9
The present embodiment Nb-Hf-Zr-TiO2Alloy bar material is made up of the raw material of following mass percent：Hf 8%, Zr 7%, TiO24%, surplus is Nb.
The present embodiment prepares Nb-Hf-Zr-TiO2The method of alloy bar material comprises the following steps：
Step 1: niobium powder, hafnium powder, zirconium powder and titanium dioxide powder are placed in ball mill, the ball under argon gas atmosphere protection Mill is well mixed, obtains mixed-powder；The rotational speed of ball-mill of the ball mill is 300r/min, the time of the ball milling of the ball mill For 15h；The granularity of the hafnium powder and zirconium powder is no more than 10 μm, and the granularity of the titanium dioxide powder is not more than 5 μm, niobium powder Granularity is not more than 20 μm；The quality purity of the hafnium powder, zirconium powder and titanium dioxide powder is not less than 99.5%, the niobium powder Quality purity is not less than 99.9%；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, it is close after the air in housing to be evacuated Capsule body；
It is 1600 DEG C in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove, pressure Power is HIP sintering 2h under conditions of 200MPa, removes housing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy sintering Body；The housing is hollow cylindrical structure, and the material of the housing is pure titanium；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1050 DEG C, extrusion ratio in extrusion temperature To be extruded under conditions of 9, the processing that strips off the skin is carried out after natural cooling, Nb-Hf-Zr-TiO is obtained2Alloy bar material.
Nb-Hf-Zr-TiO manufactured in the present embodiment2Alloy bar material room temperature tensile intensity is that 981MPa, room temperature elongation percentage are 30%, through 5 × 106Fatigue strength after secondary cycling fatigue experiment is 450MPa, and 1300 DEG C of tensile strength is 370MPa, should Nb-Hf-Zr-TiO2Alloy bar material has good temperature-room type plasticity and tensile strength, and excellent fatigue strength and high temperature it is strong Degree, the engine component that can be used in aero-turbine.
It is described above, only it is presently preferred embodiments of the present invention, any limitation is not done to the present invention, it is every according to invention skill Any simple modification, change and equivalent structure change that art is substantially made to above example, still fall within the technology of the present invention In the protection domain of scheme.

Claims (8)

1. a kind of Nb-Hf-Zr-TiO2Alloy bar material, it is characterised in that be made up of the raw material of following mass percent：Hf 2%~ 8%, Zr 3%~7%, TiO24%~10%, surplus is Nb；The Nb-Hf-Zr-TiO2The preparation method bag of alloy bar material Include following steps：
Step 1: by Nb, Hf, Zr and TiO2It is placed in ball mill, ball milling mixing is uniform under argon gas atmosphere protection, is mixed Powder；
Step 2: mixed-powder described in step one is compressing, obtain blank；
Step 3: blank described in step 2 is loaded into housing, housing is vacuumized, capsul after the air in housing to be evacuated Body；
It is 1500 DEG C~1600 in temperature Step 4: the blank being sealed in step 3 in housing is placed in high temperature insostatic pressing (HIP) stove DEG C, pressure is HIP sintering 1h~2h under conditions of 150MPa~200MPa, removes housing after natural cooling, obtains Nb- Hf-Zr-TiO2Alloy sintered compact；
Step 5: by Nb-Hf-Zr-TiO described in step 42Alloy sintered compact is 1000 DEG C~1200 DEG C in extrusion temperature, is squeezed Pressure ratio is to be extruded under conditions of 6~10, and progress strips off the skin processing after natural cooling, obtains Nb-Hf-Zr-TiO2Alloy bar material.
2. Nb-Hf-Zr-TiO according to claim 12Alloy bar material, it is characterised in that by the original of following mass percent Material is made：Hf 3%~7%, Zr 4%~6%, TiO25%~9%, surplus is Nb.
3. Nb-Hf-Zr-TiO according to claim 22Alloy bar material, it is characterised in that by the original of following mass percent Material is made：Hf 5%, Zr 5%, TiO27%, surplus is Nb.
4. the Nb-Hf-Zr-TiO according to claim 1,2 or 32Alloy bar material, it is characterised in that described Hf, Zr, TiO2 It is powder raw material with Nb, the wherein granularity of hafnium powder and zirconium powder is no more than 10 μm, and the granularity of titanium dioxide powder is not more than 5 μ M, the granularity of niobium powder is not more than 20 μm.
5. Nb-Hf-Zr-TiO according to claim 42Alloy bar material, it is characterised in that the hafnium powder, zirconium powder and dioxy The quality purity for changing titanium valve body is not less than 99.5%, and the quality purity of the niobium powder is not less than 99.9%.
6. Nb-Hf-Zr-TiO according to claim 12Alloy bar material, it is characterised in that ball mill described in step one Rotational speed of ball-mill is 200r/min~300r/min, and the time of the ball milling of the ball mill is 10h~20h.
7. Nb-Hf-Zr-TiO according to claim 12Alloy bar material, it is characterised in that housing described in step 4 is sky Heart cylindrical structural, the material of the housing is pure titanium.
8. Nb-Hf-Zr-TiO according to claim 12Alloy bar material, it is characterised in that extrusion temperature described in step 5 For 1050 DEG C~1150 DEG C, extrusion ratio is 7~9.
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