CN102888649A - Method for preparing Si-TaSi2 eutectic in-situ composite material - Google Patents

Method for preparing Si-TaSi2 eutectic in-situ composite material Download PDF

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CN102888649A
CN102888649A CN2012103827483A CN201210382748A CN102888649A CN 102888649 A CN102888649 A CN 102888649A CN 2012103827483 A CN2012103827483 A CN 2012103827483A CN 201210382748 A CN201210382748 A CN 201210382748A CN 102888649 A CN102888649 A CN 102888649A
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tasi
eutectic
coupon
eutectic alloy
heating member
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CN102888649B (en
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苏海军
张军
杨新宇
刘林
傅恒志
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Northwestern Polytechnical University
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Abstract

The invention relates to a method for preparing an Si-TaSi2 eutectic in-situ composite material. Two-zone resistance heating is used, heating bodies are respectively a tungsten heating element and a tantalum heating element, and the temperature gradient of a molten mass is increased; the temperature is kept through multilayer metal shield, radial heat radiation is inhibited, and the temperature is controlled by an infrared thermocouple to realize the accurate control on the temperature of the molten zone; and the temperature field is divided into a hot zone and a cold zone by an aluminum oxide insulating plate, thus forming strict one-way heat flow. When a sample is completely molten, the sample is drawn into Ga-In-Sn liquid metal through tension and is forcedly cooled, thus obtaining the Si-TaSi2 eutectic in-situ composite material which has ultrafine tissues and evenly-distributed TaSi2 fibers; and the property of the material is improved.

Description

A kind of Si-TaSi for preparing 2The method of eutectic autogenous composite material
Technical field
The present invention relates to field of material preparation, specifically a kind of Si-TaSi for preparing 2The method of eutectic autogenous composite material.
Background technology
Refractory metal silicide TaSi 2Has high-melting-point (T m=2040 ° of C), good oxidation-resistance, lower work function
Figure BDA00002238279200011
And good bonding strength is arranged with silicon, so Si-TaSi 2Eutectic autogenous composite material is considered to a kind of Novel cold field emission material with broad prospect of application.At present, the described Si-TaSi of preparation commonly used 2The method of eutectic autogenous composite material has following several:
1, Czochralski (CZ) method.Document " D.M.Ditchek, J.Hefter, T.R.Middleton.Microstructure of Czochralskl grown Si-TaSi 2Eutectic composites[J] .Journal of Crystal growth, 102 (1990) 401-412. " [1]Adopt the CZ directional solidification technique, prepared Si-TaSi 2The ROD EUTECTIC in-situ composite.The CZ method easily causes radially skewness of solute because seed crystal and crucible rotate the Unsteady Temperature Field of generation simultaneously, has greatly affected the field emission performance of material.
2, electron-beam floating zone melting method.Document " C.J.Cui, J.Zhang, Z.W.Jia, H.J.Su, L.Liu, H.Z.Fu.Microstructure and field emission properties of the Si-TaSi 2Eutectic in situ composites by electron beam floating zone melting technique[J] .Journal of Crystal growth, 310 (2008) 71-77. " [2]Proposed to adopt without the solid technology of the area electron beam consolidation of crucible and prepared Si-TaSi 2Eutectic autogenous composite material has improved thermograde (300～500K/cm), and obtained to organize the matrix material of comparatively refinement.Prepare Si-TaSi with this technology 2During eutectic since the temperature of melt and withdrawing rate can not be independently, the control of precision, therefore be difficult to solidified structure is optimized and quantitative design, be unfavorable for that the solidification theory that carries out this alloy studies.Electron beam also can produce stronger convection current to bombardment and the stirring in melting zone in addition, equally easily causes microstructure and composition inhomogeneous.
3, traditional Bridgman method.Document " N.J.Helbren, S.E.R.Hiscocks.Silicon-and germanium-based eutectics[J] .Journal of Materials Science, 8 (1973) 1744-1750 " [3]Proposed to prepare Si-TaSi with the Bridgman directional solidification technique 2Eutectic autogenous composite material.Because the method adopts ruhmkorff coil heating and naturally cooling, thus thermograde low＜100K/cm, solidification rate is low＜10 μ m/s, the fibrous tissue of preparation is thick and regularity is relatively poor, has greatly affected the field emission performance of material.
Summary of the invention
For overcoming the preparation Si-TaSi that exists in the prior art 2The eutectic autogenous composite material structural constituent is uneven, it is thick to organize, the problem that oriented growth is poor, and further improve the field emission performance of this material, the present invention proposes a kind of Si-TaSi of preparation 2The method of eutectic autogenous composite material.
The present invention includes following steps:
Step 1, preparation Si-TaSi 2Eutectic alloy ingot casting mother metal:
As starting material, press the eutectic composition preparation with high-purity Si and high-purity Ta, obtain the mother metal raw material, the atomic percent of Si:Ta is 99: 1 in the described mother metal raw material; Pack into the mother metal raw material in the quartz crucible and place in the smelting furnace, smelting furnace is evacuated to low vacuum in 2 * 10 -4Pa also keeps this vacuum tightness; With the smelting furnace heating, add the speed of pining for 30 ℃/min and progressively smelting furnace is heated to 1450 ℃, make the mother metal raw material melt rear insulation 30min fully; Powered-down also is cooled to room temperature with water coolant with temperature in the smelting furnace, obtains Si-TaSi 2Eutectic alloy ingot casting mother metal;
Step 2, load coupon:
With the Si-TaSi that obtains 2Eutectic alloy ingot casting mother metal cuts into coupon; Be placed on the polishing of the coupon that obtains in the spirituous solution and adopt ultrasonic cleaning 30min; The coupon that cleans up is put in the alundum tube; Operation pull system is immersed into below the crystallizer Ga-In-Sn refrigerant liquid level stainless joint fully; The aluminum oxide thermal baffle is put into stove; Close furnace chamber, and the W/Re thermopair is installed;
Step 3, Si-TaSi 2The directional freeze of eutectic alloy coupon:
Si-TaSi 2The detailed process of the directional freeze of eutectic alloy coupon is:
It is 6.6 * 10 that the directional freeze furnace chamber is evacuated to vacuum tightness -4Pa also keeps this vacuum tightness; Be filled with Ar gas in the furnace chamber to solidifying; After opening successively recirculated cooling water, thermopair, open the tungsten heating member power supply that solidifies in the stove, add the thermocoagulation furnace chamber with the speed of 15 ℃/min, simultaneously also can be to Si-TaSi 2Eutectic alloy coupon and the heating of tantalum heating member; When the temperature of tantalum heating member arrives 1000 ℃, connect tantalum heating member power supply, behind this tantalum heating member preheating 10min, be heated to 1500 ℃ and be incubated 30min by the tantalum heating member to solidifying furnace chamber; Described tantalum heating member is 10 ℃/min to the temperature rise rate that solidifies the furnace chamber heating, makes Si-TaSi 2The eutectic alloy coupon melts fully; Start pull-out mechanism, make Si-TaSi 2The eutectic alloy coupon moves from top to bottom and enters in the Ga-In-Sn liquid metal with the speed of 1～200 μ m/s, realizes the continuous directional solidification of material.
The present invention adopts the two-region resistive heating, and large tantalum heating member adopts respectively tungsten, tantalum heating unit, improves the thermograde of melt; Adopt multiple layer metal to shield insulation, suppress radially heat radiation, and by the accurate control of Infrared Thermocouple temperature control realization to the melting zone temperature; Adopt the aluminum oxide thermal baffle that the temperature field is divided into hot-zone and cold-zone, form strict unidirectional hot-fluid.After sample melts fully, with certain speed the sample pull is forced cooling in the Ga-In-Sn liquid metal, thereby obtain microstructure ultra-fining treatment, TaSi 2The uniform Si-TaSi of Fiber Distribution 2Eutectic alloy.
Among the present invention, melt temperature remains on 1500 ℃, and thermograde is 210K/cm;
The sample drawing velocity is to Si-TaSi 2The eutectic microtexture has material impact, improves the pull sweep velocity and can reduce the ROD EUTECTIC spacing, and withdrawing rate is defined as 1～200 μ m/s.
The present invention compared with prior art has the following advantages:
1) compare with traditional B ridgman with the CZ method and have high thermograde (210K/cm): the present invention adopts the two-region resistive heating, the whole heating sample of tungsten heating member, the tantalum heating member carries out the local strengthening heating in the forward position, freezing interface to melt, below thermal baffle, adopt simultaneously liquid metal to force cooling to solidifying sample, thereby obtain high thermograde; High thermograde helps to improve acquisition Si-TaSi 2The solidification rate of eutectic structure is realized the large solidification rate range regulation of tissue signature's yardstick and phase volume fraction, thereby obtains to have the eutectic composites of different performance and purposes and be conducive to carry out the solidification theory research of this eutectic alloy.The present invention makes and obtains regular Si-TaSi 2The solidification rate of eutectic structure is brought up to 200 μ m/s, obtains Si-TaSi far above traditional B ridgman and CZ method 2The maximum solidification rate numerical value (6 of eutectic solidification tissue [3]With 55 μ m/s [1]).Accompanying drawing 6 (a) shows the Si-TaSi that the present invention prepares 2Eutectic structure presents good aligning.
2) prepare Si-TaSi with electron beam 2Eutectic alloy is compared, and the present invention adopts resistive heating to eliminate the impact of forced convection on tissue, can obtain more uniformly Si-TaSi 2Eutectic structure; Adopt multiple layer metal shielding insulation, thermal baffle temperature subregion and liquid metal to force cooling to eliminate the side direction heat radiation in the process of setting, can form strict unidirectional hot-fluid, help to obtain the good solidified structure of directional effect; Can obtain the sample of large-size, such as Fig. 3; Can realize melt temperature and setting rate are independently accurately controlled, thereby the quantitative relationship between acquisition Solidification Parameters and the solidified structure helps better to control Si-TaSi 2The growth of eutectic alloy and the research of carrying out corresponding solidification theory.Table 1 shows, under equal solidification rate, and the Si-TaSi of the present invention's preparation 2Eutectic alloy shows better field emission performance (cut-in voltage is little, and a transmitter current is large).
Under the equal solidification rate of table 1, the Si-TaSi of different directional solidification technique preparation 2Field emission parameter and the performance of eutectic composites
Solidification technology The present invention EBFZM [2]
Solidification rate (50 μ m/s) 50 50
Cut-in voltage (V/ μ m) 4.2 13.8
Field transmitter current (μ A) 45.2 38.3
With respect to present traditional Bridgman method, present method is by adopting two-region resistive heating, infrared thermocouple temperature control and multiple layer metal shielding insulation, not only can realize accurately controlling melt temperature, the even stable temperature field of acquisition but also can obtain relatively high thermograde (210K/cm); Drawing mechanism adopts Integral type electromagnetic clutch, greatly improves the precision that transmission stretches; Process of setting is forced cooling by the Ga-In-Sn alloy, greatly improves the speed of cooling of sample, thereby obtains tissue, homogeneous chemical composition, fiber super-refinement and the Si-TaSi that aligns 2Eutectic autogenous composite material, the performance of raising material.
Description of drawings
Fig. 1 is schema of the present invention.
Fig. 2 is solidification rate when being 50 μ m/s, the Si-TaSi of improved Bridgman directional solidification technique preparation 2The eutectic autogenous composite material coupon.
Fig. 3 (a) is when withdrawing rate is 1 μ m/s, the Si-TaSi of improved Bridgman directional solidification technique preparation 2Eutectic autogenous composite material vertical section microtexture.
Fig. 3 (b) is when withdrawing rate is 1 μ m/s, the Si-TaSi of improved Bridgman directional solidification technique preparation 2Eutectic autogenous composite material cross section microtexture.
Fig. 4 (a) is when withdrawing rate is 50 μ m/s, the Si-TaSi of improved Bridgman directional solidification technique preparation 2Eutectic autogenous composite material vertical section microtexture.
Fig. 4 (b) is when withdrawing rate is 50 μ m/s, the Si-TaSi of improved Bridgman directional solidification technique preparation 2Eutectic autogenous composite material cross section microtexture.
Fig. 5 (a) is when withdrawing rate is 200 μ m/s, the Si-TaSi of improved Bridgman directional solidification technique preparation 2Eutectic autogenous composite material vertical section microtexture.
Fig. 5 (b) is when withdrawing rate is 200 μ m/s, the Si-TaSi of improved Bridgman directional solidification technique preparation 2Eutectic autogenous composite material cross section microtexture.
Fig. 6 is the Si-TaSi with present method preparation 2The field emission performance figure of eutectic autogenous composite material.
Embodiment
Embodiment one
The present embodiment is a kind of Si-TaSi of preparation 2The method of eutectic autogenous composite material.The present embodiment adopts device for directionally solidifying by locally and forcibly heating with resistance at high gradient, by adopting two-region resistive heating, infrared thermocouple temperature control and multiple layer metal shielding insulation, preparation Si-TaSi 2Eutectic autogenous composite material.Described device for directionally solidifying by locally and forcibly heating with resistance at high gradient is proposed by Northwestern Polytechnical University, and is open in ZL201010142263.8.
The detailed process of the present embodiment may further comprise the steps:
Step 1, preparation Si-TaSi 2Eutectic alloy ingot casting mother metal:
Take purity as 99.996% Si and the Ta of purity as 99.999% as starting material, press the eutectic composition preparation, obtain the mother metal raw material, the atomic percent of Si:Ta is 99: 1 in the described mother metal raw material.To pack in the quartz crucible and place in the smelting furnace by the mother metal raw material that the eutectic composition proportioning is mixed, smelting furnace will be evacuated to low vacuum in 2 * 10 -4Pa also keeps this vacuum tightness.With the smelting furnace heating, add the speed of pining for 30 ℃/min and progressively smelting furnace is heated to 1450 ℃, make the mother metal raw material melt rear insulation 30min fully.Powered-down also is cooled to room temperature with water coolant with temperature in the smelting furnace, obtains the Si-TaSi of Φ 62 * 100mm 2Eutectic alloy ingot casting mother metal.
Step 2, load coupon:
With the Si-TaSi that obtains 2Eutectic alloy ingot casting mother metal cuts into Φ 6.9 * 70mm coupon; Be placed on the polishing of the coupon that obtains in the spirituous solution and adopt ultrasonic cleaning 30min; Be connected in the pull system with the alundum tube of stainless joint with Φ 7 * 100mm, the coupon that cleans up is put in the alundum tube, then move the pull system, stainless joint just is immersed into below the crystallizer Ga-In-Sn refrigerant liquid level fully; With internal diameter Φ 8mm, external diameter Φ 75mm, the aluminum oxide thermal baffle of thickness 3mm is put into stove; Close furnace chamber, and the W/Re thermopair is installed.
Step 3, Si-TaSi 2The directional freeze of eutectic alloy coupon: detailed process is:
It is 6.6 * 10 that the directional freeze furnace chamber is evacuated to vacuum tightness -4Pa also keeps this vacuum tightness.Be filled with Ar gas in the furnace chamber to solidifying; After opening successively recirculated cooling water, thermopair, open the tungsten heating member power supply that solidifies in the stove, add the thermocoagulation furnace chamber with the speed of 15 ℃/min, simultaneously also can be to Si-TaSi 2Eutectic alloy coupon and the heating of tantalum heating member.
When the temperature of tantalum heating member arrives 1000 ℃, connect tantalum heating member power supply, behind this tantalum heating member preheating 10min, be heated to 1500 ℃ and be incubated 30min by the tantalum heating member to solidifying furnace chamber; Described tantalum heating member is 10 ℃/min to the temperature rise rate that solidifies the furnace chamber heating, makes Si-TaSi 2The eutectic alloy coupon melts fully.Start pull-out mechanism, make Si-TaSi 2The eutectic alloy coupon moves from top to bottom and enters in the Ga-In-Sn liquid metal with the speed of 1～200 μ m/s, realizes the continuous directional solidification of material, in the present embodiment, and Si-TaSi 2The withdrawing rate of eutectic alloy coupon is 1 μ m/s; The thermograde of directional freeze is 210K/cm.
Effect for checking the present embodiment intercepts respectively a vertical section and a cross section in the steady-state growth district of test rod, and described vertical section sample and cross section sample are carried out conventional metallographic processing.The metallographic specimen that obtains is immersed in 30 ℃, HF: HNO 3Carry out wet etching in=1: 4 corrosive fluids, etching time is 15min.Adopt scanning electron microscope (SEM) to resulting Si-TaSi 2The vertical section of sample and cross section microstructure are observed, the Si-TaSi that obtains 2The two component eutectic in-situ composite is evenly distributed mutually, and Fibre diameter is 8.36 μ m, and fiber spacing is 64.85 μ m.
Embodiment two
The present embodiment is a kind of Si-TaSi of preparation 2The method of eutectic autogenous composite material.Its detailed process may further comprise the steps:
Step 1, preparation Si-TaSi 2Eutectic alloy ingot casting mother metal:
Take purity as 99.996% Si and the Ta of purity as 99.999% as starting material, press the eutectic composition preparation, obtain the mother metal raw material, the atomic percent of Si:Ta is 99: 1 in the described mother metal raw material.To pack in the quartz crucible and place in the smelting furnace by the mother metal raw material that the eutectic composition proportioning is mixed, smelting furnace will be evacuated to low vacuum in 2 * 10 -4Pa also keeps this vacuum tightness.With the smelting furnace heating, add the speed of pining for 30 ℃/min and progressively smelting furnace is heated to 1450 ℃, make the mother metal raw material melt rear insulation 30min fully.Powered-down also is cooled to room temperature with water coolant with temperature in the smelting furnace, obtains the Si-TaSi of Φ 62 * 100mm 2Eutectic alloy ingot casting mother metal.
Step 2, load coupon:
With the Si-TaSi that obtains 2Eutectic alloy ingot casting mother metal cuts into Φ 6.9 * 70mm coupon; Be placed on the polishing of the coupon that obtains in the spirituous solution and adopt ultrasonic cleaning 30min; Be connected in the pull system with the alundum tube of stainless joint with Φ 7 * 100mm, the coupon that cleans up is put in the alundum tube, then move the pull system, stainless joint just is immersed into below the crystallizer Ga-In-Sn refrigerant liquid level fully; With internal diameter Φ 8mm, external diameter Φ 75mm, the aluminum oxide thermal baffle of thickness 3mm is put into stove; Close furnace chamber, and the W/Re thermopair is installed.
Step 3, Si-TaSi 2The directional freeze of eutectic alloy coupon: detailed process is:
It is 6.6 * 10 that the directional freeze furnace chamber is evacuated to vacuum tightness -4Pa also keeps this vacuum tightness.Be filled with Ar gas in the furnace chamber to solidifying; After opening successively recirculated cooling water, thermopair, open the tungsten heating member power supply that solidifies in the stove, add the thermocoagulation furnace chamber with the speed of 15 ℃/min, simultaneously also can be to Si-TaSi 2Eutectic alloy coupon and the heating of tantalum heating member.
When the temperature of tantalum heating member arrives 1000 ℃, connect tantalum heating member power supply, behind this tantalum heating member preheating 10min, be heated to 1500 ℃ and be incubated 30min by the tantalum heating member to solidifying furnace chamber; Described tantalum heating member is 10 ℃/min to the temperature rise rate that solidifies the furnace chamber heating, makes Si-TaSi 2The eutectic alloy coupon melts fully.Start pull-out mechanism, make Si-TaSi 2The eutectic alloy coupon moves from top to bottom and enters in the Ga-In-Sn liquid metal with the speed of 1～200 μ m/s, realizes the continuous directional solidification of material, in the present embodiment, and Si-TaSi 2The withdrawing rate of eutectic alloy coupon is 10 μ m/s; The thermograde of directional freeze is 210K/cm.
Be the effect of checking the present embodiment, intercept respectively a vertical section and a cross section in the steady-state zone of test rod, and described vertical section sample and cross section sample are carried out conventional metallographic process.The metallographic specimen that obtains is immersed in 30 ℃, HF: HNO 3Carry out wet etching in=1: 4 corrosive fluids, etching time is 15min.Adopt scanning electron microscope (SEM) to resulting Si-TaSi 2The vertical section of sample and cross section microstructure are observed, the Si-TaSi that obtains 2The two component eutectic in-situ composite is evenly distributed mutually, and Fibre diameter is 12.20 μ m, and fiber spacing is 36.81 μ m.
Embodiment three
The present embodiment is a kind of Si-TaSi of preparation 2The method of eutectic autogenous composite material.Its detailed process may further comprise the steps:
Step 1, preparation Si-TaSi 2Eutectic alloy ingot casting mother metal:
Take purity as 99.996% Si and the Ta of purity as 99.999% as starting material, press the eutectic composition preparation, obtain the mother metal raw material, the atomic percent of Si:Ta is 99: 1 in the described mother metal raw material.To pack in the quartz crucible and place in the smelting furnace by the mother metal raw material that the eutectic composition proportioning is mixed, smelting furnace will be evacuated to low vacuum in 2 * 10 -4Pa also keeps this vacuum tightness.With the smelting furnace heating, add the speed of pining for 30 ℃/min and progressively the heating power of smelting furnace is increased to 1450 ℃, make the mother metal raw material melt rear insulation 30min fully.Powered-down also is cooled to room temperature with water coolant with temperature in the smelting furnace, obtains the Si-TaSi of Φ 62 * 100mm 2Eutectic alloy ingot casting mother metal.
Step 2, load coupon:
With the Si-TaSi that obtains 2Eutectic alloy ingot casting mother metal cuts into Φ 6.9 * 70mm coupon; Be placed on the polishing of the coupon that obtains in the spirituous solution and adopt ultrasonic cleaning 30min; Be connected in the pull system with the alundum tube of stainless joint with Φ 7 * 100mm, the coupon that cleans up is put in the alundum tube, then move the pull system, stainless joint just is immersed into below the crystallizer Ga-In-Sn refrigerant liquid level fully; With internal diameter Φ 8mm, external diameter Φ 75mm, the aluminum oxide thermal baffle of thickness 3mm is put into stove; Close furnace chamber, and the W/Re thermopair is installed.
Step 3, Si-TaSi 2The directional freeze of eutectic alloy coupon: detailed process is:
It is 6.6 * 10 that the directional freeze furnace chamber is evacuated to vacuum tightness -4Pa also keeps this vacuum tightness.Be filled with Ar gas in the furnace chamber to solidifying; After opening successively recirculated cooling water, thermopair, open the tungsten heating member power supply that solidifies in the stove, add the thermocoagulation furnace chamber with the speed of 15 ℃/min, simultaneously also can be to Si-TaSi 2Eutectic alloy coupon and the heating of tantalum heating member.
When the temperature of tantalum heating member arrives 1000 ℃, connect tantalum heating member power supply, behind this tantalum heating member preheating 10min, be heated to 1500 ℃ and be incubated 30min by the tantalum heating member to solidifying furnace chamber; Described tantalum heating member is 10 ℃/min to the temperature rise rate that solidifies the furnace chamber heating, makes Si-TaSi 2The eutectic alloy coupon melts fully.Start pull-out mechanism, make Si-TaSi 2The eutectic alloy coupon moves from top to bottom and enters in the Ga-In-Sn liquid metal with the speed of 1～200 μ m/s, realizes the continuous directional solidification of material, in the present embodiment, and Si-TaSi 2The withdrawing rate of eutectic alloy coupon is 50 μ m/s; The thermograde of directional freeze is 210K/cm.
Be the effect of checking the present embodiment, and and embodiment two compare, intercept respectively a cross section and a cross section in the steady-state zone of test rod, and described vertical section sample and cross section sample carried out conventional metallographic process.The metallographic specimen that obtains is immersed in 30 ℃, HF: HNO 3Carry out wet etching in=1: 4 corrosive fluids, etching time is 15min.Adopt scanning electron microscope (SEM) to resulting Si-TaSi 2The vertical section of sample and cross section microstructure are observed, the Si-TaSi that obtains 2The two component eutectic in-situ composite is evenly distributed mutually, obviously reduces than diameter and the spacing of embodiment two fibers, and Fibre diameter is 3 μ m, and fiber spacing is 6.51 μ m.
Embodiment four
The present embodiment is a kind of Si-TaSi of preparation 2The method of eutectic autogenous composite material.Its detailed process may further comprise the steps:
Step 1, preparation Si-TaSi 2Eutectic alloy ingot casting mother metal:
Take purity as 99.996% Si and the Ta of purity as 99.999% as starting material, press the eutectic composition preparation, obtain the mother metal raw material, the atomic percent of Si:Ta is 99: 1 in the described mother metal raw material.To pack in the quartz crucible and place in the smelting furnace by the mother metal raw material that the eutectic composition proportioning is mixed, smelting furnace will be evacuated to low vacuum in 2 * 10 -4Pa also keeps this vacuum tightness.With the smelting furnace heating, add the speed of pining for 30 ℃/min and progressively the heating power of smelting furnace is increased to 1450 ℃, make the mother metal raw material melt rear insulation 30min fully.Powered-down also is cooled to room temperature with water coolant with temperature in the smelting furnace, obtains the Si-TaSi of Φ 62 * 100mm 2Eutectic alloy ingot casting mother metal.
Step 2, load coupon:
With the Si-TaSi that obtains 2Eutectic alloy ingot casting mother metal cuts into Φ 6.9 * 70mm coupon; Be placed on the polishing of the coupon that obtains in the spirituous solution and adopt ultrasonic cleaning 30min; Be connected in the pull system with the alundum tube of stainless joint with Φ 7 * 100mm, the coupon that cleans up is put in the alundum tube, then move the pull system, stainless joint just is immersed into below the crystallizer Ga-In-Sn refrigerant liquid level fully; With internal diameter Φ 8mm, external diameter Φ 75mm, the aluminum oxide thermal baffle of thickness 3mm is put into stove; Close furnace chamber, and the W/Re thermopair is installed.
Step 3, Si-TaSi 2The directional freeze of eutectic alloy coupon: detailed process is:
It is 6.6 * 10 that the directional freeze furnace chamber is evacuated to vacuum tightness -4Pa also keeps this vacuum tightness.Be filled with Ar gas in the furnace chamber to solidifying; After opening successively recirculated cooling water, thermopair, open the tungsten heating member power supply that solidifies in the stove, add the thermocoagulation furnace chamber with the speed of 15 ℃/min, simultaneously also can be to Si-TaSi 2Eutectic alloy coupon and the heating of tantalum heating member.
When the temperature of tantalum heating member arrives 1000 ℃, connect tantalum heating member power supply, behind this tantalum heating member preheating 10min, be heated to 1500 ℃ and be incubated 30min by the tantalum heating member to solidifying furnace chamber; Described tantalum heating member is 10 ℃/min to the temperature rise rate that solidifies the furnace chamber heating, makes Si-TaSi 2The eutectic alloy coupon melts fully.Start pull-out mechanism, make Si-TaSi 2The eutectic alloy coupon moves from top to bottom and enters in the Ga-In-Sn liquid metal with the speed of 1～200 μ m/s, realizes the continuous directional solidification of material, in the present embodiment, and Si-TaSi 2The withdrawing rate of eutectic alloy coupon is 100 μ m/s; The thermograde of directional freeze is 210K/cm.
Be the effect of checking the present embodiment, and and embodiment two compare, intercept respectively a cross section and a cross section in the steady-state zone of test rod, and described vertical section sample and cross section sample carried out conventional metallographic process.The metallographic specimen that obtains is immersed in 30 ℃, HF: HNO 3Carry out wet etching in=1: 4 corrosive fluids, etching time is 15min.Adopt scanning electron microscope (SEM) to resulting Si-TaSi 2The vertical section of sample and cross section microstructure are observed, the Si-TaSi that obtains 2The two component eutectic in-situ composite is evenly distributed mutually, obviously reduces than diameter and the spacing of embodiment two fibers, and Fibre diameter is 1.37 μ m, and fiber spacing is 3.83 μ m.
Embodiment five
The present embodiment is a kind of Si-TaSi of preparation 2The method of eutectic autogenous composite material.Its detailed process may further comprise the steps:
Step 1, preparation Si-TaSi 2Eutectic alloy ingot casting mother metal:
Take purity as 99.996% Si and the Ta of purity as 99.999% as starting material, press the eutectic composition preparation, obtain the mother metal raw material, the atomic percent of Si:Ta is 99: 1 in the described mother metal raw material.To pack in the quartz crucible and place in the smelting furnace by the mother metal raw material that the eutectic composition proportioning is mixed, smelting furnace will be evacuated to low vacuum in 2 * 10 -4Pa also keeps this vacuum tightness.With the smelting furnace heating, add the speed of pining for 30 ℃/min and progressively the heating power of smelting furnace is increased to 1450 ℃, make the mother metal raw material melt rear insulation 30min fully.Powered-down also is cooled to room temperature with water coolant with temperature in the smelting furnace, obtains the Si-TaSi of Φ 62 * 100mm 2Eutectic alloy ingot casting mother metal.
Step 2, load coupon:
With the Si-TaSi that obtains 2Eutectic alloy ingot casting mother metal cuts into Φ 6.9 * 70mm coupon; Be placed on the polishing of the coupon that obtains in the spirituous solution and adopt ultrasonic cleaning 30min; Be connected in the pull system with the alundum tube of stainless joint with Φ 7 * 100mm, the coupon that cleans up is put in the alundum tube, then move the pull system, stainless joint just is immersed into below the crystallizer Ga-In-Sn refrigerant liquid level fully; With internal diameter Φ 8mm, external diameter Φ 75mm, the aluminum oxide thermal baffle of thickness 3mm is put into stove; Close furnace chamber, and the W/Re thermopair is installed.
Step 3, Si-TaSi 2The directional freeze of eutectic alloy coupon: detailed process is:
It is 6.6 * 10 that the directional freeze furnace chamber is evacuated to vacuum tightness -4Pa also keeps this vacuum tightness.Be filled with Ar gas in the furnace chamber to solidifying; After opening successively recirculated cooling water, thermopair, open the tungsten heating member power supply that solidifies in the stove, add the thermocoagulation furnace chamber with the speed of 15 ℃/min, simultaneously also can be to Si-TaSi 2Eutectic alloy coupon and the heating of tantalum heating member.
When the temperature of tantalum heating member arrives 1000 ℃, connect tantalum heating member power supply, behind this tantalum heating member preheating 10min, be heated to 1500 ℃ and be incubated 30min by the tantalum heating member to solidifying furnace chamber; Described tantalum heating member is 10 ℃/min to the temperature rise rate that solidifies the furnace chamber heating, makes Si-TaSi 2The eutectic alloy coupon melts fully.Start pull-out mechanism, make Si-TaSi 2The eutectic alloy coupon moves from top to bottom and enters in the Ga-In-Sn liquid metal with the speed of 1～200 μ m/s, realizes the continuous directional solidification of material, in the present embodiment, and Si-TaSi 2The withdrawing rate of eutectic alloy coupon is 200 μ m/s; The thermograde of directional freeze is 210K/cm.
Be the effect of checking the present embodiment, and and embodiment two compare, intercept respectively a cross section and a cross section in the steady-state zone of test rod, and described vertical section sample and cross section sample carried out conventional metallographic process.The metallographic specimen that obtains is immersed in 30 ℃, HF: HNO 3Carry out wet etching in=1: 4 corrosive fluids, etching time is 15min.Adopt scanning electron microscope (SEM) to resulting Si-TaSi 2The vertical section of sample and cross section microstructure are observed, the Si-TaSi that obtains 2The two component eutectic in-situ composite is evenly distributed mutually, obviously reduces than diameter and the spacing of embodiment two fibers, and Fibre diameter is 1.17 μ m, and fiber spacing is 3.09 μ m.

Claims (1)

1. one kind prepares Si-TaSi 2The method of eutectic autogenous composite material is characterized in that, may further comprise the steps:
Step 1, preparation Si-TaSi 2Eutectic alloy ingot casting mother metal:
As starting material, press the eutectic composition preparation with high-purity Si and high-purity Ta, obtain the mother metal raw material, the atomic percent of Si:Ta is 99: 1 in the described mother metal raw material; Pack into the mother metal raw material in the quartz crucible and place in the smelting furnace, smelting furnace is evacuated to low vacuum in 2 * 10 -4Pa also keeps this vacuum tightness; With the smelting furnace heating, add the speed of pining for 30 ℃/min and progressively smelting furnace is heated to 1450 ℃, make the mother metal raw material melt rear insulation 30min fully; Powered-down also is cooled to room temperature with water coolant with temperature in the smelting furnace, obtains Si-TaSi 2Eutectic alloy ingot casting mother metal;
Step 2, load coupon:
With the Si-TaSi that obtains 2Eutectic alloy ingot casting mother metal cuts into coupon; Be placed on the polishing of the coupon that obtains in the spirituous solution and adopt ultrasonic cleaning 30min; The coupon that cleans up is put in the alundum tube; Operation pull system is immersed into below the crystallizer Ga-In-Sn refrigerant liquid level stainless joint fully; The aluminum oxide thermal baffle is put into stove; Close furnace chamber, and the W/Re thermopair is installed;
Step 3, Si-TaSi 2The directional freeze of eutectic alloy coupon:
Si-TaSi 2The detailed process of the directional freeze of eutectic alloy coupon is:
It is 6.6 * 10 that the directional freeze furnace chamber is evacuated to vacuum tightness -4Pa also keeps this vacuum tightness; Be filled with Ar gas in the furnace chamber to solidifying; After opening successively recirculated cooling water, thermopair, open the tungsten heating member power supply that solidifies in the stove, add the thermocoagulation furnace chamber with the speed of 15 ℃/min, simultaneously also can be to Si-TaSi 2Eutectic alloy coupon and the heating of tantalum heating member;
When the temperature of tantalum heating member arrives 1000 ℃, connect tantalum heating member power supply, behind this tantalum heating member preheating 10min, be heated to 1500 ℃ and be incubated 30min by the tantalum heating member to solidifying furnace chamber; Described tantalum heating member is 10 ℃/min to the temperature rise rate that solidifies the furnace chamber heating, makes Si-TaSi 2The eutectic alloy coupon melts fully; Start pull-out mechanism, make Si-TaSi 2The eutectic alloy coupon moves from top to bottom and enters in the Ga-In-Sn liquid metal with the speed of 1～200 μ m/s, realizes the continuous directional solidification of material.
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Publication number Priority date Publication date Assignee Title
CN108796253A (en) * 2018-04-24 2018-11-13 西北工业大学 A kind of preparation of reactive infiltration Si-Y alloys and tissue modulation method
CN113649532A (en) * 2021-08-19 2021-11-16 西安建筑科技大学 Low-cost preparation of Ni-Ni3Method for producing Si eutectic autogenous composite material
CN114527009A (en) * 2022-02-09 2022-05-24 南京钢铁股份有限公司 Melting and solidifying process control method on thermal simulation testing machine

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CN102703971A (en) * 2012-06-01 2012-10-03 西北工业大学 Method for preparing Si-based binary eutectic in-situ composites

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CN101797639A (en) * 2010-04-08 2010-08-11 西北工业大学 Device for directionally solidifying by locally and forcibly heating with resistance at high gradient
CN102703971A (en) * 2012-06-01 2012-10-03 西北工业大学 Method for preparing Si-based binary eutectic in-situ composites

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Publication number Priority date Publication date Assignee Title
CN108796253A (en) * 2018-04-24 2018-11-13 西北工业大学 A kind of preparation of reactive infiltration Si-Y alloys and tissue modulation method
CN113649532A (en) * 2021-08-19 2021-11-16 西安建筑科技大学 Low-cost preparation of Ni-Ni3Method for producing Si eutectic autogenous composite material
CN114527009A (en) * 2022-02-09 2022-05-24 南京钢铁股份有限公司 Melting and solidifying process control method on thermal simulation testing machine
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