CN102534279A - In situ reaction hot-pressing method for manufacturing intermetallic compound T2 phase alloys - Google Patents

In situ reaction hot-pressing method for manufacturing intermetallic compound T2 phase alloys Download PDF

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CN102534279A
CN102534279A CN2012100195320A CN201210019532A CN102534279A CN 102534279 A CN102534279 A CN 102534279A CN 2012100195320 A CN2012100195320 A CN 2012100195320A CN 201210019532 A CN201210019532 A CN 201210019532A CN 102534279 A CN102534279 A CN 102534279A
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intermetallic compound
situ
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CN102534279B (en
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张来启
潘昆明
王珏
林均品
叶丰
郝国建
梁永峰
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

An in situ reaction hot-pressing method for manufacturing intermetallic compound T2 phase alloys belongs to technical field of ally material manufacturing. The in situ reaction hot-pressing method is characterized by adopting a spark plasma sintering (SPS) furnace to eliminate low temperature solid-solid reaction among three elements of Mo, Si and B mainly through control of technological parameters, utilizing solid-liquid reaction among the three elements to in situ synthesize a T2 phase, fully using heat released by in-situ reaction, simultaneously hot-pressing compactly by one step, reducing hot-pressing temperature, improving material density, refining tissues, simplifying processes, and utilizing advantages that an in situ synthesis interface is clean, free of Mo3Si, Mo5Si3, Mo2B, MoB and other leading phases and high in purity to manufacture the T2 phase alloys with small crystal particle and high compactness and purity. Therefore good high temperature oxidation resistance, excellent mechanical properties and particularly high temperature mechanical properties of the T2 phase are exerted to the maximum limit, properties of the T2 phase alloys are improved to the maximum limit, and the in situ reaction hot-pressing method for manufacturing intermetallic compound T2 phase alloys is simple and convenient in process, easy to control and simplified in working procedure.

Description

A kind of reaction in hot-press method for preparing intermetallic compound T2 phase alloy
 
Technical field
The invention belongs to the alloy material preparing technical field, particularly the preparation of HMP, infusible intermetallic compound silicon molybdenum compound.
Background technology
T2 has high fusing point (~ 2200 ℃), low relatively density (8.864g/cm mutually 3), excellent hot strength, good high-temperature creep resistance and oxidation drag, good thermal conductivity and electroconductibility, be considered to have in aerospace and the gas turbine engine field ultrahigh-temperature of new generation (1200-1600 ℃) structured material of broad prospect of application.But, because its cubic D8 1(less between Composition Region, therefore the little atom of solid solution limited in one's ability, proposed very high requirement to preparing high-purity and fine and close T2 phase alloy technology for tI32, I4/mcm) crystalline structure.
At present, the preparation method of T2 phase alloy mainly contains arc melting+annealing process, mechanical alloying etc.Wherein, adopt arc melting+annealing process (Nunes C A, et al. Intermetallics, 2000,8:327-337; Rawn C J, et al. Intermetallics, 2001,9:209-216) preparation the T2 phase alloy organize thick, the uneven segregation of composition is serious, occurs Mo inevitably 3Si, Mo 5Si 3, Mo 2Leading phase such as B, MoB, and contain tiny crack in the tissue; Mechanical alloying (Yamauchi A, et al. J. Alloy. Compd., 2007,434-435:420-423; Abbasi A R, et al. Mater. Sci. Eng. A, 2011; A528:3295-3301) be that powder is realized viscous deformation, cold welding, fragmentation under high energy ball mill; Thereby reach the physical and chemical process of atomic level alloying between element, therefore very difficult accurately control reaction process is reacted not exclusively and the shortage moulding process; In order to obtain fine and close T2 phase alloy, need to add follow-up densification operation.Mo in the T2 phase alloy of above-mentioned these prepared 3Si, Mo 5Si 3, Mo 2High temperature oxidation resistance and the mechanical property that the appearance of leading phase such as B, MoB can reduce material be mechanical behavior under high temperature especially; And organize thick, inhomogeneous and tiny crack also to be unfavorable for the improvement of T2 phase alloy mechanical property; The mechanical alloy metallization processes also needs follow-up fine and close operations such as hot pressing, and preparation section is many, and control is complicated.
Summary of the invention
The objective of the invention is to utilize the reaction in heat pressing process; Through controlling its processing parameter; Tiny, the high densification of preparation crystal grain, high-purity T2 phase alloy; Thereby good resistance high temperature oxidation stability and the excellent mechanical property of bringing into play the T2 phase to greatest extent be mechanical behavior under high temperature especially, improves T2 phase alloy performance to greatest extent, and technology easy, be easy to control, simplified working procedures.
The present invention adopts the SPS sintering oven, mainly through control process parameters, eliminates the low temperature solid-solid reaction between Mo, Si and the B element; And utilize the synthetic T2 phase of solid-liquid reaction original position between them, and it is fine and close to make full use of the step hot pressing simultaneously of reaction in liberated heat, reduces hot pressing temperature; Improve material density; Thinning microstructure is simplified working process, and brings into play original position synthetic interface cleaning simultaneously, does not contain Mo 3Si, Mo 5Si 3, Mo 2Leading phase such as B, MoB, the advantage that purity is high prepare tiny, the high densification of crystal grain, high-purity T2 phase alloy.(6.23 μ m, 99.999wt%) (its one-tenth is grouped into by Mo raw material involved in the present invention for 3.63 μ m, 99.99wt%) mixture with the B powder from Mo powder (5.96 μ m, 99.99 wt%), Si powder 5SiB 2The interval preparation of stoichiometric composition, through comprehensive ball mill ball milling 15-30h (is medium with the absolute ethyl alcohol), afterwards at 50 ℃ of vacuum-drying 8-12h.
The concrete preparation process of T2 phase alloy is following:
(1) (6.23 μ m, 99.999wt%) (3.63 μ m are raw material 99.99wt%), press Mo with the B powder with Mo powder (5.96 μ m, 99.99 wt%), Si powder 5SiB 2The stoichiometric composition interval make required mixed powder; Its atomic percent is: 61.5-63.0%Mo, 12.0-14.0%Si and 23.5-25.5%B; Through comprehensive ball mill with 300 rev/mins of ball milling 15-30h (is medium with the absolute ethyl alcohol), then at 50 ℃ of vacuum-drying 8-12h.
(2) on the SPS sintering oven, carry out reaction in hot pressing; Temperature rise rate is 100-300 ℃/min, and sintering temperature is 1450-1600 ℃, and soaking time is 5-30min; Exert pressure and be 40-60MPa; After sintering is accomplished, be cooled to 400-500 ℃ with the speed of 10-20 ℃/min, last stove is chilled to room temperature.Release gradually after pressurize is arrived 1100-1200 ℃ in process of cooling.Whole sintering process is carried out under vacuum condition.
The invention has the advantages that and utilize the reaction in heat pressing process, on the SPS sintering oven, mainly pass through control process parameters; Eliminate the low temperature solid-solid reaction between Mo, Si and the B element, and utilize the synthetic T2 phase of solid-liquid reaction original position between them, and it is fine and close to make full use of the step hot pressing simultaneously of reaction in liberated heat; Reduce hot pressing temperature, improve material density, thinning microstructure; Simplify working process, bring into play original position synthetic interface cleaning simultaneously, do not contain Mo 3Si, Mo 5Si 3, Mo 2Leading phase such as B, MoB, the advantage that purity is high; Prepare tiny, the high densification of crystal grain, high-purity T2 phase alloy; Therefore, good resistance high temperature oxidation stability and the excellent mechanical property that this T2 phase alloy can be brought into play the T2 phase to greatest extent be mechanical behavior under high temperature especially, improves its performance to greatest extent.Because the present invention only need control the reaction in hot pressing parameters, reaction in synthetic with hot-pressing densification simultaneously a step accomplish, need not follow-up secondary densification technique, thus technology easy, be easy to control, simplified working procedures.
 
Description of drawings
Fig. 1 is Mo-13Si-25B, 200 ℃/min temperature rise rate, 1500 ℃ of sintering temperature T2 phase alloy XRD spectral lines;
Fig. 2 is Mo-13Si-25B, 200 ℃/min temperature rise rate, 1500 ℃ of sintering temperature T2 phase alloy crystal grain distribution plans;
Fig. 3 is Mo-13Si-25B, 200 ℃/min temperature rise rate, 1500 ℃ of sintering temperature T2 phase alloy differing temps three-point bending fracture toughness;
Fig. 4 is Mo-13Si-25B, 200 ℃/min temperature rise rate, 1500 ℃ of sintering temperature T2 phase alloy differing temps compression true stress-true strain curves;
Fig. 5 is Mo-14Si-23.5B, 100 ℃/min temperature rise rate, 1500 ℃ of sintering temperature T2 phase alloy XRD spectral lines;
Fig. 6 is Mo-12Si-25.5B, 200 ℃/min temperature rise rate, 1450 ℃ of sintering temperature T2 phase alloy XRD spectral lines.
Embodiment
Embodiment 1:The nominal composition of mixed powder is that (atomic percent, %), with 300 rev/mins of ball milling 24h (is medium with the absolute ethyl alcohol), 50 ℃ of vacuum-drying 9h weigh 62.66g to Mo-13Si-25B through comprehensive ball mill.Adopt the SPS-1500 agglomerating plant, load weighted powder is inserted in the graphite jig that internal diameter is 30mm, temperature rise rate is 200 ℃/min, and sintering temperature is 1500 ℃, and soaking time is 7min, exerts pressure to be 60MPa.After sintering is accomplished, be cooled to 500 ℃ with the speed of 20 ℃/min, last stove is chilled to room temperature.Release gradually after the pressurize to 1200 ℃ in process of cooling.Whole sintering process is carried out under vacuum condition, finally obtains Φ 30mm * 10mm appearance base.Fig. 1 is the XRD spectral line of T2 phase alloy, does not find Mo 3Si, Mo 5Si 3, Mo 2B, MoB etc. are leading to be existed mutually, and purity is high, obviously is superior to arc melting+annealing process (Nunes C A, et al. Intermetallics, 2000,8:327-337; Rawn C J, et al. Intermetallics, 2001,9:209-216) and mechanical alloying (Yamauchi A, et al. J. Alloy. Compd., 2007,434-435:420-423; Abbasi A R, et al. Mater. Sci. Eng. A, 2011, A528:3295-3301).The relative density of this T2 phase alloy is ~ 99.5%, and average grain size is 1.44 μ m (Fig. 2), is significantly less than arc melting+annealing process (Nunes C A, et al. Intermetallics, 2000,8:327-337; Rawn C J, et al. Intermetallics, 2001,9:209-216).The T2 phase alloy has good mechanical performance (Fig. 3-4), room temperature, 1200 ℃ of three-point bending fracture toughness K ICBe respectively 3.41MPam 1/2With 9.66 MPam 1/2(Fig. 3), room temperature, 1200 ℃, 1400 ℃ compressive strengths are respectively 2905MPa, 965MPa and 483MPa (Fig. 4).
Embodiment 2:The nominal composition of mixed powder is that (atomic percent, %), with 300 rev/mins of ball milling 24h (is medium with the absolute ethyl alcohol), 50 ℃ of vacuum-drying 9h weigh 62.66g to Mo-14Si-23.5B through comprehensive ball mill.Adopt the SPS-1500 agglomerating plant, load weighted powder is inserted in the graphite jig that internal diameter is 30mm, temperature rise rate is 100 ℃/min, and sintering temperature is 1500 ℃, and soaking time is 7min, exerts pressure to be 60MPa.After sintering is accomplished, be cooled to 500 ℃ with the speed of 20 ℃/min, last stove is chilled to room temperature.Release gradually after the pressurize to 1200 ℃ in process of cooling.Whole sintering process is carried out under vacuum condition, finally obtains Φ 30mm * 10mm appearance base.Fig. 5 is the XRD spectral line of this technology T2 phase alloy sample, can find out and only contain the T2 phase in the alloy, does not find Mo 3Si, Mo 5Si 3, Mo 2B, MoB etc. are leading to be existed mutually, and purity is high, obviously is superior to arc melting+annealing process (Nunes C A, et al. Intermetallics, 2000,8:327-337; Rawn C J, et al. Intermetallics, 2001,9:209-216) and mechanical alloying (Yamauchi A, et al. J. Alloy. Compd., 2007,434-435:420-423; Abbasi A R, et al. Mater. Sci. Eng. A, 2011, A528:3295-3301).
Embodiment 3:The nominal composition of mixed powder is that (atomic percent, %), with 300 rev/mins of ball milling 24h (is medium with the absolute ethyl alcohol), 50 ℃ of vacuum-drying 9h weigh 62.66g to Mo-12Si-25.5B through comprehensive ball mill.Adopt the SPS-1500 agglomerating plant, load weighted powder is inserted in the graphite jig that internal diameter is 30mm, temperature rise rate is 200 ℃/min, and sintering temperature is 1450 ℃, and soaking time is 7min, exerts pressure to be 60MPa.After sintering is accomplished, be cooled to 500 ℃ with the speed of 20 ℃/min, last stove is chilled to room temperature.Release gradually after the pressurize to 1200 ℃ in process of cooling.Whole sintering process is carried out under vacuum condition, finally obtains Φ 30mm * 10mm appearance base.Fig. 6 is the XRD spectral line of this technology T2 phase alloy sample, can find out and only contain the T2 phase in the alloy, does not find Mo 3Si, Mo 5Si 3, Mo 2B, MoB etc. are leading to be existed mutually, and purity is high, obviously is superior to arc melting+annealing process (Nunes C A, et al. Intermetallics, 2000,8:327-337; Rawn C J, et al. Intermetallics, 2001,9:209-216) and mechanical alloying (Yamauchi A, et al. J. Alloy. Compd., 2007,434-435:420-423; Abbasi A R, et al. Mater. Sci. Eng. A, 2011, A528:3295-3301).

Claims (2)

1. a reaction in hot-press method for preparing intermetallic compound T2 phase alloy is characterized in that utilizing the hot pressing of SPS sintering oven reaction in to prepare tiny, the high densification of crystal grain, high-purity T2 phase alloy; Press Mo 5SiB 2The required mixed powder of the interval preparation of stoichiometric composition, its atomic percent is: 61.5-63.0%Mo, 12.0-14.0%Si and 23.5-25.5%B; The hot pressed technology of reaction in is: temperature rise rate 100-300 ℃/min, and sintering temperature 1450-1600 ℃, soaking time 5-30min; 40-60MPa exerts pressure; After sintering is accomplished, be cooled to 400-500 ℃ with the speed of 10-20 ℃/min, last stove is chilled to room temperature; Release gradually after pressurize is arrived 1100-1200 ℃ in process of cooling.
2. the reaction in hot-press method of preparation intermetallic compound T2 phase alloy as claimed in claim 1, the preparation that it is characterized in that mixed powder is by Mo 5SiB 2The interval preparation of stoichiometric composition, and be medium with the absolute ethyl alcohol, through comprehensive ball mill with 300 rev/mins of ball milling 15-30h, afterwards at 50 ℃ of vacuum-drying 8-12h.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103938010A (en) * 2014-04-23 2014-07-23 北京科技大学 Method for preparing porous molybdenum-silicon-boron three-phase alloy
CN103952581A (en) * 2014-04-23 2014-07-30 北京科技大学 Method for preparing high-porosity molybdenum-silicon-boron porous material by adding pore-forming agent
CN104550904A (en) * 2014-12-17 2015-04-29 武汉理工大学 Novel TiAl-based self-lubricating material using Mo-B-O tabular crystals as lubricating phase and preparation method
CN111020259A (en) * 2019-11-18 2020-04-17 海南大学 Flaky intermetallic compound reinforced fine-grain tungsten alloy and preparation method thereof
CN114653950A (en) * 2022-02-28 2022-06-24 金堆城钼业光明（山东）股份有限公司 Molybdenum-silicon-boron solid solution reinforced molybdenum cutting wire and preparation method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103938010A (en) * 2014-04-23 2014-07-23 北京科技大学 Method for preparing porous molybdenum-silicon-boron three-phase alloy
CN103952581A (en) * 2014-04-23 2014-07-30 北京科技大学 Method for preparing high-porosity molybdenum-silicon-boron porous material by adding pore-forming agent
CN103938010B (en) * 2014-04-23 2015-10-28 北京科技大学 A kind of method preparing porous molybdenum silicon boron triple-phase alloys
CN104550904A (en) * 2014-12-17 2015-04-29 武汉理工大学 Novel TiAl-based self-lubricating material using Mo-B-O tabular crystals as lubricating phase and preparation method
CN104550904B (en) * 2014-12-17 2016-09-14 武汉理工大学 A kind of with Mo-B-O platelike crystal be the lubrication novel TiAl based self-lubricating material of phase and preparation method
CN111020259A (en) * 2019-11-18 2020-04-17 海南大学 Flaky intermetallic compound reinforced fine-grain tungsten alloy and preparation method thereof
CN111020259B (en) * 2019-11-18 2021-11-23 海南大学 Flaky intermetallic compound reinforced fine-grain tungsten alloy and preparation method thereof
CN114653950A (en) * 2022-02-28 2022-06-24 金堆城钼业光明（山东）股份有限公司 Molybdenum-silicon-boron solid solution reinforced molybdenum cutting wire and preparation method thereof

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