CN108866414A - A kind of high tough molybdenum alloy and preparation method - Google Patents

A kind of high tough molybdenum alloy and preparation method Download PDF

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CN108866414A
CN108866414A CN201810593712.7A CN201810593712A CN108866414A CN 108866414 A CN108866414 A CN 108866414A CN 201810593712 A CN201810593712 A CN 201810593712A CN 108866414 A CN108866414 A CN 108866414A
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powder
molybdenum alloy
molybdenum
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hydride
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CN108866414B (en
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王快社
胡卜亮
胡平
邓洁
周宇航
李世磊
陈文静
夏雨
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Xian University of Architecture and Technology
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04Alloys based on tungsten or molybdenum
    • B22F1/0003
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
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    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • C22C1/058Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-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
    • C22C32/0005Non-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 at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
    • B22F2003/185Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers by hot rolling, below sintering temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

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Abstract

The present invention provides a kind of high tough molybdenum alloys to be prepared from the following raw materials based on parts by weight:Titantium hydride is 5~20 parts, and zircoium hydride is 0.8~2 part, and magnesium powder is 0.2~0.4 part, and molybdenum powder is 1000 parts;Or titantium hydride is 5~20 parts, hydrogenation hafnium is 0.8~2 part, and magnesium powder is 0.2~0.4 part, and molybdenum powder is 1000 parts.The good combination property of the tough molybdenum alloy of height of the invention, room temperature tensile intensity are greater than 1200MPa, and elongation is greater than 8.0%.The present invention is by the stronger Mg element of reproducibility as reducing agent, it on the one hand can be in conjunction with oxygen, the content of harmful element oxygen in molybdenum system is effectively reduced, it reduces C element reduction and generates the hole that gas generates, generate in the segregation of intrinsic silicon and with matrix the influence of the second coarse phase, on the other hand, Mg element and oxygen element can form the magnesia hardening constituent with high-temperature stability.The magnesia phase of tetragonal is similar to body-centred cubic Mo substrate structure, and coherence or half coherence crystallography relationship can be formed with matrix, and Strengthening and Toughening effect is significant.

Description

A kind of high tough molybdenum alloy and preparation method
Technical field
The invention belongs to field of powder metallurgy, are related to molybdenum alloy, and in particular to a kind of high tough molybdenum alloy and preparation method.
Background technique
There is molybdenum the advantages that elevated temperature strength is high, fusing point is high, and thermal conductivity is good, corrosion resistance and good be widely used in it Electronics glass closure material, nuclear power cladding nuclear fuels material, heater heat generating component, medical instrument rotary anode, the illiteracy of aerospace Skin material, the important components such as nozzle of engine.But molybdenum seriously limits the use of molybdenum alloy because of black brittleness, and it is crisp to influence low temperature The main reason for property is wherein oxygen, the segregation of nitrogen and high porosity.Therefore, oxygen, nitrogen reinforcing and low hole are developed and used The novel molybdenum alloy of gap rate is raising molybdenum alloy performance and improves molybdenum alloy production technology, improves product quality to be molybdenum alloy research The Main way that person and the producer make great efforts.
It is main to be realized by incorporation internal oxidation alloying in the method for design molybdenum alloy and improvement molybdenum alloy performance. Wherein TZM alloy mainly passes through Ti, Zr solution strengthening and forms second-phase strength, rare-earth oxide doping molybdenum alloys with C element Mainly by rare earth oxide doping strengthen, existing dipping molybdenum alloy mainly by incorporation hardening constituent based on, they it is each leisure not Same application field shows superior performance.With the development of modern industry, the single performance of molybdenum alloy cannot be at present The requirement for meeting client, to mechanical behavior under high temperature, low temperature moulding, high toughness and high recrystallization temperature excellent combination property Molybdenum alloy exploitation and preparation seem very necessary and urgently.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of high tough molybdenum alloy and preparation side Method, solves that molybdenum alloy performance in the prior art is single, the technical problem of comprehensive performance deficiency.
In order to solve the above-mentioned technical problem, the present invention is realised by adopting the following technical scheme:
A kind of high tough molybdenum alloy, including following raw material are made:Titantium hydride, zircoium hydride, magnesium powder and molybdenum powder;Or titantium hydride, Hydrogenate hafnium, magnesium powder and molybdenum powder.
Specifically, based on parts by weight, being prepared from the following raw materials:Titantium hydride is 5~20 parts, and zircoium hydride is 0.8~2 part, Magnesium powder is 0.2~0.4 part, and molybdenum powder is 1000 parts;
Or titantium hydride is 5~20 parts, hydrogenation hafnium is 0.8~2 part, and magnesium powder is 0.2~0.4 part, and molybdenum powder is 1000 parts.
The room temperature tensile intensity of the tough molybdenum alloy of height is greater than 1200MPa, and elongation is greater than 8.0%.
The present invention also has following technical characteristic:
The present invention also protects a kind of preparation method of high tough molybdenum alloy, and this method is closed using high tough molybdenum as described above Gold formula.
This method includes the following steps:
Step 1, a mixing:According to formula rate ingredient, titantium hydride, zircoium hydride or hydrogenation hafnium and magnesium powder are used three Tie up batch mixer mixing 1h;
Step 2, rerolling:Titantium hydride, zircoium hydride or hydrogenation hafnium and magnesium powder and molybdenum powder are mixed again by what is be uniformly mixed Close 2~4h;
Step 3, ball milling:Powder after rerolling is packed into ball grinder, is filled with argon gas, is not higher than 200r/ in revolving speed Ball milling 2h in the low energy ball mill of min;
Step 4, compacting:Powder cold isostatic compaction after ball milling, pressing pressure 180MPa, dwell time 15min;
Step 5, sintering:By the blank obtained after compacting multi-steps sintering in a hydrogen atmosphere, heat up 6h to 900 DEG C, then 2h is kept the temperature, is heated up 2h to 1200 DEG C, 3h is then kept the temperature, is heated up 3h to 1600 DEG C, 2h is then kept the temperature, is heated up 2h to 1900 DEG C, so After keep the temperature 6h;
Step 6, rolling:To sintering blank rolling deformation, 1200 DEG C of cogging temperature, it is thick to roll rear plate for total deformation 90% Spend 1.0mm.
Compared with prior art, the present invention having the following technical effect that:
(I) good combination property of the tough molybdenum alloy of height of the invention, room temperature tensile intensity are greater than 1200MPa, and elongation is big In 8.0%.
(II) in terms of composition design, in TZM and MHC alloy system, on the one hand C element needs to form an oxidation in conjunction with oxygen Matrix is discharged in carbon or carbon dioxide gas, on the other hand, C element hardening constituent oxide particle is restored to be formed it is carbide reinforced Phase.But the gas that C element is formed can generate hole in intrinsic silicon, C element is easy to be segregated, and can generate with Mo substrate coarse Mo2C generates adverse effect to the mechanical property of molybdenum alloy.
By the stronger Mg element of reproducibility, as reducing agent, on the one hand molybdenum can be effectively reduced in conjunction with oxygen in the present invention The content of harmful element oxygen in system, reduce C element reduction generate gas generate hole, intrinsic silicon segregation and with Matrix generates the influence of the second coarse phase, and on the other hand, Mg element and oxygen element can form the oxidation with high-temperature stability Magnesium fortified phase.The magnesia phase of tetragonal is similar to body-centred cubic Mo substrate structure, and coherence or half can be formed with matrix Coherence crystallography relationship, Strengthening and Toughening effect are significant.
(III) in preparation method, traditional TZM alloy is mainly that the solution strengthening of Ti, Zr/Hf element plays invigoration effect, because This prevents TiH2、ZrH2/HfH2The key for being oxidized into the high tough molybdenum alloy of preparation.Traditional preparation methods pass through full element powder A last mixing-ball milling-compacting-sintering-processing is prepared, due to TiH2、ZrH2/HfH2, magnesium elements easily aoxidize, Magnesium elements are relative to TiH2、ZrH2/HfH2With stronger reproducibility, TiH2、ZrH2/HfH2It can be effective when being coexisted with magnesium elements Prevent TiH2、ZrH2/HfH2Oxidation.Therefore, this preparation uses a mixing, first by TiH2、ZrH2/HfH2It is mixed with Mg machinery It closes, can be improved TiH2、ZrH2/HfH2With the distribution that coexists of Mg, furthermore by rerolling by TiH2、ZrH2/HfH2It is mixed with Mg It closes material to mix with molybdenum powder, TiH is again prevented from using argon gas protection ball milling2、ZrH2/HfH2, Mg and molybdenum powder aoxidize, it is mixed to improve powder The uniformity of conjunction.Be conducive to TiH2、ZrH2/HfH2Pyrolytic simultaneously generates the second phase of effective solution strengthening and high-temperature oxydation magnesium Formation.
Detailed description of the invention
Fig. 1 is high tough molybdenum alloy stress strain curve.
Fig. 2 is the SEM photograph of high tough molybdenum alloy.
Explanation is further explained in detail to particular content of the invention with reference to embodiments.
Specific embodiment
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited to implement in detail below Example, all equivalent transformations made on the basis of the technical solutions of the present application each fall within protection scope of the present invention.
Embodiment 1:
The present embodiment provides a kind of high tough molybdenum alloy and is prepared from the following raw materials based on parts by weight:Titantium hydride is 5.0g, zircoium hydride 0.8g, magnesium powder 0.4g, molybdenum powder 1000g.
The preparation method of the tough molybdenum alloy of height of the present embodiment includes the following steps:
Step 1, a mixing:According to formula rate ingredient, titantium hydride, zircoium hydride and magnesium powder are used into three-dimensional material mixer Mix 1h;
Step 2, rerolling:Titantium hydride, zircoium hydride and magnesium powder are mixed into 2~4h with molybdenum powder again by what is be uniformly mixed;
Step 3, ball milling:Powder after rerolling is packed into ball grinder, is filled with argon gas, is not higher than 200r/ in revolving speed Ball milling 2h in the low energy ball mill of min;
Step 4, compacting:Powder cold isostatic compaction after ball milling, pressing pressure 180MPa, dwell time 15min;
Step 5, sintering:By the blank obtained after compacting multi-steps sintering in a hydrogen atmosphere, heat up 6h to 900 DEG C, then 2h is kept the temperature, is heated up 2h to 1200 DEG C, 3h is then kept the temperature, is heated up 3h to 1600 DEG C, 2h is then kept the temperature, is heated up 2h to 1900 DEG C, so After keep the temperature 6h;
Step 6, rolling:To sintering blank rolling deformation, 1200 DEG C of cogging temperature, it is thick to roll rear plate for total deformation 90% Spend 1.0mm.
The tough molybdenum alloy stress strain curve of height of the present embodiment is as shown in Figure 1, the SEM of the tough molybdenum alloy of height of the present embodiment shines Piece is as shown in Figure 2.
The room temperature tensile intensity of height made from the present embodiment is tough molybdenum alloy is 1215MPa, elongation 8.2%.
Comparative example 1:
The present embodiment provides a kind of tough molybdenum alloy and is prepared from the following raw materials based on parts by weight:Titantium hydride is 5.0g, hydrogen Change zirconium is 0.8g, carbon dust 0.4g, molybdenum powder 1000g.The magnesium powder in the formula of embodiment 1 is replaced with into carbon dust.
The preparation method of the molybdenum alloy of this comparative example is substantially the same manner as Example 1.
The room temperature tensile intensity of molybdenum alloy made from this comparative example is 1026MPa, elongation 7.5%.
Comparative example 2:
The present embodiment provides a kind of tough molybdenum alloy, is formulated identical as the formula of embodiment 1.Difference is the molybdenum of this comparative example The preparation method of alloy is different from embodiment 1.
The preparation method of the molybdenum alloy of this comparative example includes the following steps:
Step 1, mixing:According to formula rate ingredient, by titantium hydride, zircoium hydride, magnesium powder and with molybdenum powder three-dimensional blender is used Machine mixes 3~5h;
Step 2, ball milling:Powder after rerolling is packed into ball grinder, is filled with argon gas, is not higher than 400r/ in revolving speed Ball milling 2h in the low energy ball mill of min;
Step 3, compacting:It is essentially identical with the step of embodiment 1 four.
Step 4, sintering:The blank obtained after compacting is sintered under vacuum atmosphere, 1900 DEG C of sintering temperature, when sintering Between 30 hours, furnace cooling obtains molybdenum alloy material;
Step 5, rolling:It is essentially identical with the step of embodiment 1 six.
The room temperature tensile intensity of molybdenum alloy made from this comparative example is 1084MPa, elongation 7.8%.
Comparative example 3:
The present embodiment provides a kind of tough molybdenum alloy, and difference is, the formula preparation method of this comparative example with embodiment 1 not Together.
The formula of this comparative example is identical as comparative example 1.
The preparation method of the molybdenum alloy of this comparative example and comparative example 2 are essentially identical.
The room temperature tensile intensity of molybdenum alloy made from this comparative example is 965MPa, elongation 6.8%.
Embodiment 2:
The present embodiment provides a kind of high tough molybdenum alloy and is prepared from the following raw materials based on parts by weight:Titantium hydride is 10.0g, zircoium hydride 1.0g, magnesium powder 0.2g, molybdenum powder 1000g.
The preparation method of the tough molybdenum alloy of height of the present embodiment is substantially the same manner as Example 1.
The tough molybdenum alloy stress strain curve of height and Fig. 1 of the present embodiment are essentially identical, the tough molybdenum alloy of height of the present embodiment SEM photograph is essentially identical with Fig. 2.
The room temperature tensile intensity of height made from the present embodiment is tough molybdenum alloy is 1223MPa, elongation 8.2%.
Embodiment 3:
The present embodiment provides a kind of high tough molybdenum alloy and is prepared from the following raw materials based on parts by weight:Titantium hydride is 20.0g, zircoium hydride 2.0g, magnesium powder 0.4g, molybdenum powder 1000g.
The preparation method of the tough molybdenum alloy of height of the present embodiment is substantially the same manner as Example 1.
The tough molybdenum alloy stress strain curve of height and Fig. 1 of the present embodiment are essentially identical, the tough molybdenum alloy of height of the present embodiment SEM photograph is essentially identical with Fig. 2.
The room temperature tensile intensity of height made from the present embodiment is tough molybdenum alloy is 1226MPa, elongation 8.1%.
Embodiment 4:
The present embodiment provides a kind of high tough molybdenum alloy and is prepared from the following raw materials based on parts by weight:Titantium hydride is 5.0g, hydrogenation hafnium are 0.8g, magnesium powder 0.4g, molybdenum powder 1000g.
The preparation method of the tough molybdenum alloy of height of the present embodiment is substantially the same manner as Example 1.
The tough molybdenum alloy stress strain curve of height and Fig. 1 of the present embodiment are essentially identical, the tough molybdenum alloy of height of the present embodiment SEM photograph is essentially identical with Fig. 2.
The room temperature tensile intensity of height made from the present embodiment is tough molybdenum alloy is 1247MPa, elongation 8.3%.
Embodiment 5:
The present embodiment provides a kind of high tough molybdenum alloy and is prepared from the following raw materials based on parts by weight:Titantium hydride is 10.0g, hydrogenation hafnium are 1.0g, magnesium powder 0.2g, molybdenum powder 1000g.
The preparation method of the tough molybdenum alloy of height of the present embodiment is substantially the same manner as Example 1.
The tough molybdenum alloy stress strain curve of height and Fig. 1 of the present embodiment are essentially identical, the tough molybdenum alloy of height of the present embodiment SEM photograph is essentially identical with Fig. 2.
The room temperature tensile intensity of height made from the present embodiment is tough molybdenum alloy is 1257MPa, elongation 8.3%.
Embodiment 6:
The present embodiment provides a kind of high tough molybdenum alloy and is prepared from the following raw materials based on parts by weight:Titantium hydride is 20.0g, hydrogenation hafnium are 2.0g, magnesium powder 0.4g, molybdenum powder 1000g.
The preparation method of the tough molybdenum alloy of height of the present embodiment is substantially the same manner as Example 1.
The tough molybdenum alloy stress strain curve of height and Fig. 1 of the present embodiment are essentially identical, the tough molybdenum alloy of height of the present embodiment SEM photograph is essentially identical with Fig. 2.
The room temperature tensile intensity of height made from the present embodiment is tough molybdenum alloy is 1284MPa, elongation 8.6%.

Claims (5)

1. a kind of high tough molybdenum alloy, which is characterized in that be made including following raw material:Titantium hydride, zircoium hydride, magnesium powder and molybdenum powder; Or titantium hydride, hydrogenation hafnium, magnesium powder and molybdenum powder.
2. high tough molybdenum alloy as described in claim 1, which is characterized in that based on parts by weight, be prepared from the following raw materials:Hydrogen Changing titanium is 5~20 parts, and zircoium hydride is 0.8~2 part, and magnesium powder is 0.2~0.4 part, and molybdenum powder is 1000 parts;
Or titantium hydride is 5~20 parts, hydrogenation hafnium is 0.8~2 part, and magnesium powder is 0.2~0.4 part, and molybdenum powder is 1000 parts.
3. high tough molybdenum alloy as described in claim 1, which is characterized in that the room temperature tensile of the tough molybdenum alloy of height is strong Degree is greater than 1200MPa, and elongation is greater than 8.0%.
4. a kind of preparation method of high tough molybdenum alloy, which is characterized in that this method is using as claimed in claim 2 high tough Molybdenum alloy formula.
5. the preparation method of high tough molybdenum alloy as claimed in claim 4, which is characterized in that this method includes the following steps:
Step 1, a mixing:According to formula rate ingredient, titantium hydride, zircoium hydride or hydrogenation hafnium and magnesium powder are used three-dimensional mixed Material machine mixing 1h;
Step 2, rerolling:Titantium hydride, zircoium hydride or hydrogenation hafnium and magnesium powder are mixed 2 with molybdenum powder again by what is be uniformly mixed ~4h;
Step 3, ball milling:Powder after rerolling is packed into ball grinder, is filled with argon gas, in revolving speed not higher than 200r/min's Ball milling 2h in low energy ball mill;
Step 4, compacting:Powder cold isostatic compaction after ball milling, pressing pressure 180MPa, dwell time 15min;
Step 5, sintering:By the blank obtained after compacting, in a hydrogen atmosphere then multi-steps sintering, 6h to 900 DEG C of heating are kept the temperature 2h heats up 2h to 1200 DEG C, then keeps the temperature 3h, heats up 3h to 1600 DEG C, then keeps the temperature 2h, heats up 2h to 1900 DEG C, then protects Warm 6h;
Step 6, rolling:To sintering blank rolling deformation, 1200 DEG C of cogging temperature, total deformation 90% rolls rear plate thickness 1.0mm。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102041402A (en) * 2009-10-23 2011-05-04 西安格美金属材料有限公司 Preparation method of low-oxygen molybdenum alloy and application thereof
CN104651696A (en) * 2015-03-13 2015-05-27 潍坊学院 TiC dispersion-strengthened molybdenum alloy and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102041402A (en) * 2009-10-23 2011-05-04 西安格美金属材料有限公司 Preparation method of low-oxygen molybdenum alloy and application thereof
CN104651696A (en) * 2015-03-13 2015-05-27 潍坊学院 TiC dispersion-strengthened molybdenum alloy and preparation method thereof

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