CN112404449A - Device and method for continuously synthesizing powder material based on thermal shock - Google Patents

Device and method for continuously synthesizing powder material based on thermal shock Download PDF

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Publication number
CN112404449A
CN112404449A CN202011160025.XA CN202011160025A CN112404449A CN 112404449 A CN112404449 A CN 112404449A CN 202011160025 A CN202011160025 A CN 202011160025A CN 112404449 A CN112404449 A CN 112404449A
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conductive substrate
contact electrode
precursor
carbon
thermal shock
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熊宇杰
席大为
龙冉
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • 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
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926Copper and noble metals
    • B01J35/40
    • 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
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/054Nanosized particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/02Alloys containing less than 50% by weight of each constituent containing copper

Abstract

An apparatus and method for continuously synthesizing powder material based on thermal shock, the apparatus comprising: the wall of the cavity is provided with an inlet port, an outlet port and an air hole, and a contact electrode is arranged inside the cavity; the conductive substrate is in movable surface contact connection with the contact electrode and used for carrying a precursor of a material to be thermally treated, wherein the material to be thermally treated comprises a powder material or a load-type powder material, and the conductive substrate penetrates through the inlet and outlet ports; the traction assembly is connected with the conductive substrate so as to draw the conductive substrate and the precursor carrying the material to be thermally treated to continuously or intermittently move in the cavity; the conducting wire is connected with the contact electrode and an external power supply, and the conducting wire, the contact electrode, the external power supply and the conductive substrate form a closed loop; the precursor of the material to be heat-treated is carried on the drawn conductive substrate and drawn into a high-temperature area to be subjected to thermal shock treatment. The device and the method can realize continuous thermal shock treatment of the ultra-large batch powder material or the load type powder material.

Description

Device and method for continuously synthesizing powder material based on thermal shock
Technical Field
The invention relates to the field of material preparation, belongs to a production line type preparation scheme, and particularly relates to a device and a method for continuously synthesizing a nano powder material based on thermal shock.
Background
Electrothermal impact is the heat generated by passing a direct current through an electrically conductive material (W ═ I)2Rt), which is characterized in that the conductive material is often thin and light and has small specific heat, so that the ambient temperature of the conductive material can be raised to 1000-3000 ℃ in millisecond-level time under the condition of large current, thereby achieving red brightness. After a short heat treatment, the power-off moment can make the conductive material surround by 105The temperature is rapidly reduced at the temperature reduction rate of the degree of C/s, so that novel functional materials which cannot be obtained in conventional heating and sintering modes (such as a tubular furnace, a muffle furnace, microwave heating and the like) can be obtained. The nano material which is difficult to prepare by the conventional method is obtained by the novel rapid thermal shock method, so that the nano material has wide application prospect and draws wide attention of academical circles.
The related art proposes a production process of a tempered glass insulator, which requires production of a tempered glass element through cold and hot impact. The related art also proposes an electrothermal-based nano-welding method, in which after a suitable voltage is applied between two metal probes, the tips of the two probes are brought into contact, and a current is passed through the two probes to generate heat, so that the nano-material in contact with one of the two probes is melted or the tip of the one probe is melted, thereby welding the tips of the metal probes and the nano-material. However, this method is limited in the types of processing materials to which it is applicable and has a low yield. In large thermal shock equipment, in order to obtain equipment with high energy efficiency, the related technology provides a cold and hot shock system and a cold and hot shock machine with the cold and hot shock system, so that the problems of slow temperature rise and reduction and high energy consumption of the existing cold and hot shock system are solved, the temperature can be quickly reduced and increased by using shock gas at the temperature of-80-225 ℃, preheating and pre-cooling are not needed, and liquid nitrogen assistance is not needed. But the temperature range of the scheme is narrow, and the method is useless for a plurality of high-temperature synthesis processes. In addition, the electrothermal impact synthesis methods reported so far all use fixed electrodes to clamp or bond carbon fibers and the electrodes by using silver glue, only a very small amount of centimeter-sized materials can be processed each time, the preparation yield is low, each round of operation needs to be bonded and taken, and the bonding and taking are often carried out in a glove box. High use condition and low single yield. Can only be processed in batches, and assembly and disassembly are still complicated.
Disclosure of Invention
Technical problem to be solved
Aiming at the technical problems in the prior art, the invention provides a device and a method for synthesizing a powder material based on thermal shock, which are used for at least partially solving the technical problems.
(II) technical scheme
The invention provides a device for continuously synthesizing functional materials based on thermal shock, which comprises: a cavity 101, wherein the wall of the cavity 101 is provided with an inlet port 102 and an outlet port 103, and a contact electrode 105 is arranged inside the cavity; the conductive substrate 107 is connected with the contact electrode 105 in a movable surface contact manner, and the conductive substrate 107 penetrates through the inlet and outlet port 102, wherein the conductive substrate 107 is used for carrying a precursor of a material to be thermally treated, and the material to be thermally treated comprises a powder material and a load-type powder material; the traction assembly 106 is connected with the conductive substrate 107 so as to draw the conductive substrate 107 and the precursor carrying the material to be thermally treated to continuously or intermittently move in the cavity 101; and a lead 104, wherein the lead 104 connects the contact electrode 105 with an external power supply, and the lead 104, the contact electrode 105, the external power supply and the conductive substrate 107 form a closed loop.
Optionally, the contact electrode 105 and the pulling element 106 are provided with a groove, and the conductive substrate 107 is disposed in the groove.
Optionally, the conductive substrate 107 is a single-layer conductive substrate or a double-layer conductive substrate or a multi-layer conductive substrate.
Optionally, the material of the conductive substrate 107 includes: at least one of carbon cloth, carbon paper, carbon fiber, pressed carbon felt, carbon fiber film and tungsten foil; or compounding at least one of carbon cloth, carbon paper, carbon fiber, pressed carbon felt, carbon fiber film and tungsten foil with the high-temperature-resistant insulating substrate; the material to be heat-treated comprises at least one of carbon black, activated carbon, titanium oxide, tungsten oxide, aluminum oxide, silicon oxide, cerium oxide, cuprous oxide, zeolite, carbon nitride, tantalum nitride, titanium nitride, gallium nitride, cobalt phosphide and iron nickel phosphide.
Alternatively, the conductive substrate 107 may have a width in the range of 5-100mm, a thickness in the range of 0.1-4mm, and a conductivity in the range of 1-1000m Ω/cm.
Alternatively, the contact electrode 105 may comprise an electrode sheet or an electrode rod or a brush or an electrode clamp or an electrode plate or a metal pulley or a graphite pulley, and the contact electrode 105 and the conductive substrate 107 are in continuous direct contact or intermittently clamp the conductive substrate 107 by intermittent opening and closing during the movement of the conductive substrate 107.
Optionally, the external power supply is a direct current power supply, the rated voltage range is 1-200V, the rated current range is 1-50A, and the direct current pulse frequency is 0.1-20 Hz.
Another aspect of the present invention provides a method for synthesizing functional nanomaterial based on the above apparatus for continuously synthesizing functional nanomaterial based on thermal shock, comprising: carrying a precursor of a material to be heat-treated on the conductive substrate 107; the conductive substrate 107 carrying the precursor of the material to be heat-treated is drawn to move along the contact electrode 105, so that the precursor of the material to be heat-treated continuously or intermittently passes through the heating section under a preset atmosphere.
Optionally, the heating section employs a continuous heating mode or a batch heating mode; the preset atmosphere comprises nitrogen, argon, hydrogen, carbon dioxide or a local atmosphere generated when an additive for thermal reaction added in a precursor of a material to be thermally treated is thermally decomposed or gasified, wherein the additive comprises at least one of elemental boron, elemental phosphorus, elemental sulfur, urea, melamine, or vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten, silver, gold, ruthenium, rhodium, palladium, iridium, platinum, gallium and indium, chloride, nitrate, acetate or acetylacetone salt.
Optionally, the drawing speed of the drawn conductive substrate 107 carrying the material to be heat-treated is 0.1-10cm/s, and the single-time energization heating time is 0.1-10 s.
(III) advantageous effects
The invention provides a device and a method for continuously synthesizing powder materials based on thermal shock, which at least have the following beneficial effects:
the conductive substrate which can be connected with the contact electrode in a movable surface contact mode and can be pulled is arranged in the cavity to carry a precursor of the material to be thermally treated, the conductive substrate carrying the precursor of the material to be thermally treated is pulled to move along the contact electrode, so that the precursor of the material to be thermally treated continuously or intermittently passes through the heating section in a preset atmosphere, and the continuous or intermittent electrothermal impact of the heating section enables the conductive substrate and the precursor of the material to be thermally treated carried to be subjected to continuous rapid heating-high-temperature thermal treatment-rapid annealing, so that the continuous thermal impact treatment of the ultra-large-batch powder material or load-type powder material can be realized, and the device has low requirement, is easy to integrate in a production line and is suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram illustrating a structure of an apparatus for continuously synthesizing powder material based on thermal shock according to an embodiment of the present invention;
FIG. 2 schematically illustrates a top view of an apparatus for continuously synthesizing powder material based on thermal shock according to an embodiment of the present invention;
FIG. 3 is a schematic diagram illustrating a structure of an apparatus for loading a precursor of a material to be thermally processed on a single-layer drawn conductive substrate according to an embodiment of the present invention;
fig. 4 is a schematic diagram illustrating a structure of an apparatus for carrying a precursor of a material to be heat-treated on a pulled double-layer conductive substrate according to an embodiment of the present invention;
FIG. 5 schematically illustrates three views of a corresponding rubbing-type surface-contacted contact electrode structure when a single-layer conductive substrate is employed, in accordance with an embodiment of the present invention;
FIG. 6 schematically illustrates three views of a corresponding roller-type surface contact electrode structure provided by an embodiment of the invention when a single conductive substrate is used;
FIG. 7 schematically illustrates three views of a corresponding rubbing-type surface-contacted contact electrode structure when a double-layer conductive substrate is employed, according to an embodiment of the present invention;
FIG. 8 schematically illustrates three views of a corresponding roller-type surface contact electrode structure provided by an embodiment of the present invention when a double-layer conductive substrate is used;
FIG. 9 is a flow chart schematically illustrating a method for continuously synthesizing powder material based on thermal shock according to an embodiment of the present invention;
fig. 10 schematically shows an SEM image of the synthesized supported alloy nanoparticles of example 1;
FIG. 11 schematically shows an EDX mapping diagram of the synthesized supported alloy nanoparticles of example 1;
fig. 12 schematically shows an SEM image of an oxide ceramic prepared from the sintered powder of example 2.
[ reference numerals ]
101-chamber, 102-inlet and outlet ports, 103-gas holes, 104-wire, 105-contact electrode, 106-pulling assembly, 107-conductive substrate, 201-precursor of material to be heat treated, 202-precursor of material to be heat treated in heating section, 203-processing finished sample material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
Fig. 1 schematically shows a structural diagram of an apparatus for continuously synthesizing a powder material based on thermal shock according to an embodiment of the present invention, fig. 2 schematically shows a plan view of the apparatus for continuously synthesizing a powder material based on thermal shock according to an embodiment of the present invention, fig. 3 schematically shows a structural diagram of an apparatus for mounting a precursor of a material to be heat-treated on a single-layered conductive substrate according to an embodiment of the present invention, and fig. 4 schematically shows a structural diagram of an apparatus for mounting a precursor of a material to be heat-treated on a double-layered conductive substrate according to an embodiment of the present invention. It should be noted that the drawings only show a partial configuration of the main apparatus of the present invention, and do not show configurations such as a motor, a vacuum pump, and a gas path.
Referring to fig. 1-4, the apparatus for continuously synthesizing powder material based on thermal shock may include: the chamber 101 has an inlet/outlet port 102 and a gas hole 103 on its wall, a contact electrode 105 is provided inside the chamber, and the gas hole 103 is used for introducing a target gas into the chamber 101. And the conductive substrate 107 is connected with the contact electrode 105 in a movable surface contact manner, and the conductive substrate 107 penetrates through the inlet and outlet ports 102, wherein the conductive substrate 107 is used for carrying a precursor of a material to be thermally treated, and the material to be thermally treated can comprise a powder material and a supported powder material. And the traction assembly 106, wherein the traction assembly 106 is connected with the conductive substrate 107 so as to draw the conductive substrate 107 and the precursor of the carried material to move continuously or intermittently in the cavity 101. And a lead 104 connecting the contact electrode 105 and an external power source, wherein the lead 104, the contact electrode 105, the external power source and the conductive substrate 107 form a closed loop.
In a feasible manner of the embodiment of the present invention, the material of the conductive substrate 107 may be at least one of carbon cloth, carbon paper, carbon fiber, pressed carbon felt, carbon fiber film, tungsten foil, or a composite of the above materials and other high temperature resistant insulating substrates, for example, carbon cloth may be preferred. The conductive substrate 107 should generally have a strength, be tensile tractable, and be stable at high temperatures. The conductive substrate 107 is mounted on the pulling assembly 106, and the conductive substrate passes through the cavity through the hole 102 and passes through the hole 105, so that the conductive substrate 107 in the middle section of the hole 105 forms a closed loop with the contact electrode 105, the lead wire 104 and the direct current power supply. The pulling element 106 and the contact electrode 105 are for example provided with a groove, respectively, in which the conductive substrate 107 can be placed to avoid the conductive substrate falling off when the pulling element 106 rotates.
In a feasible manner of the embodiment of the present invention, the conductive substrate 107 may be, for example, a single-layer conductive substrate, a double-layer conductive substrate, or a multi-layer conductive substrate. The single-layer conductive substrate and the double-layer conductive substrate or the multi-layer conductive substrate have slightly different carrying modes of precursors of materials to be thermally processed.
When the conductive substrate 107 is a single layer, as shown in fig. 3, a precursor of the material to be thermally processed can be directly attached to the surface of the conductive layer, and in this case, the contact electrode 105 is typically a friction type or rolling type surface contact electrode (as shown in fig. 5 or fig. 6).
As shown in fig. 4, when the conductive substrate 107 is a double layer, a precursor of the material to be heat-treated may be sandwiched between two layers of conductive substrates, and at this time, both the upper and lower layers of conductive substrates are connected in parallel to a circuit, and the contact electrode 105 generally adopts upper and lower double layer surface contact electrodes, and respectively achieves surface contact with the upper and lower layers of conductive substrates (as shown in fig. 7 or fig. 8). The double-layer conductive substrate or the multi-layer conductive substrate can obtain a more uniform and stable temperature field compared to a single-layer conductive substrate.
In a possible embodiment of the present invention, the contact electrode 105, whether it is a friction type or rolling type surface contact electrode, or an upper and lower double-layer surface contact electrode, may include, for example, an electrode plate, an electrode bar, an electrode brush, an electrode clamp, an electrode plate, a metal pulley, a graphite pulley, or the like. In the moving process of the drawn conductive substrate 107 carrying the precursor of the material to be thermally treated, the contact electrode 105 and the drawn conductive substrate 107 carrying the material to be thermally treated can be continuously and directly contacted or intermittently clamp the drawn conductive substrate 107 carrying the precursor of the material to be thermally treated in an intermittent opening and closing manner, so as to realize continuous heating or intermittent heating.
In a possible embodiment of the present invention, the external power source is generally a dc power source, the rated voltage range may be, for example, 1-200V, the rated current range may be, for example, 1-50A, and the dc pulse frequency may be, for example, 0.1-20 Hz.
The device provided by the embodiment of the present disclosure can be applied to various materials to be heat-treated, including but not limited to one or more of carbon black, activated carbon, titanium oxide, tungsten oxide, aluminum oxide, silicon oxide, cerium oxide, cuprous oxide, zeolite, carbon nitride, tantalum nitride, titanium nitride, gallium nitride, cobalt phosphide and iron nickel phosphide. An additive can be additionally added into the precursor of the material to be thermally treated to realize thermal reaction. The additive may be, for example, one or more of elemental boron, elemental phosphorus, elemental sulfur, urea, melamine, or vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten, silver, gold, ruthenium, rhodium, palladium, iridium, platinum, gallium, indium, bismuth, metal chloride salts, nitrate salts, acetate salts, or acetylacetonate salts.
Based on the device for continuously synthesizing the powder material based on the thermal shock, the embodiment of the invention also provides a method for continuously synthesizing the powder material based on the thermal shock.
Fig. 9 schematically shows a flowchart of a method for continuously synthesizing powder material based on thermal shock according to an embodiment of the present invention.
As shown in fig. 9, the method may include, for example, operations S901-S902.
In operation S901, a precursor of a material to be heat-treated is carried on a drawn conductive substrate.
In the embodiment of the invention, the precursor of the material to be thermally treated is carried on the conductive substrate before the conductive substrate is drawn into the heating zone, and the precursor of the material to be thermally treated can be carried in a manner of dripping, drying, spreading powder and placing or plugging the powder into an interlayer.
In operation S902, the conductive substrate is drawn to move along the contact electrode, and the precursor of the material to be heat-treated is continuously or intermittently passed through the heating section under the preset atmosphere.
In the embodiment of the invention, after the precursor of the material to be thermally treated is carried on the conductive substrate, voltage is applied to the conductive substrate, and the precursor of the material carried on the conductive substrate of the heating section is subjected to rapid thermal shock treatment by generating heat through current. Specifically, during operation, the system is in a preset atmosphere protection state through an air passage connected to the device. The predetermined atmosphere may include, for example, a local atmosphere generated when nitrogen or argon or hydrogen or carbon dioxide or an additive for thermal reaction added to a precursor of the material to be heat-treated is thermally decomposed or gasified. The pulling assembly 106 is typically coupled to a drive motor and the conductive substrate material is pulled on both sides or one side by the pulling assembly 106. The conductive substrate carried on the conductive substrate continuously passes through the surfaces of the two contact electrodes 105, at the moment, a certain voltage is applied to the conductive substrate 107 which is in contact with the surfaces of the contact electrodes 105 and is carried with a precursor of a material to be subjected to heat treatment through the lead 104, the carried material is promoted to be subjected to heat treatment through the generated heat, and the material passing through the middle section of the contact electrode 105 is continuously subjected to heat treatment along with the continuous work of the traction assembly 106, so that the continuous production of thermal shock synthetic nano materials is realized.
In the embodiment of the invention, the drawing mode can be continuous or intermittent, and the heating mode of the corresponding heating section can also be continuous, intermittent or periodically changed. In the continuous traction heating mode, the traction speed may be, for example, 0.1 to 10 cm/s. In the intermittent traction intermittent heating mode, after traction is stopped and heat treatment is carried out for 0.1-20s, power is cut off, the part of the conductive substrate 107 carrying the material to be heat treated is pulled to enter the conductive section, traction is stopped, and then electric heat treatment is carried out. In the continuous pulling intermittent heating mode, the pulling speed may be, for example, 0.1 to 10 cm/s. Generally, the pulling speed and the thermal shock time can be controlled by adjusting the speed of the pulling assembly 106, with the wheel speed being 0.1-10cm/s, e.g., 0.1cm/s, 1cm/s, 2cm/s, 6cm/s, 10cm/s, etc. It should be noted that the apparatus may also be used to prepare the material statically or intermittently, for example, without rotating the pulling member 106, but with a voltage applied directly to the conductive substrate therebetween, as the present invention is not limited thereto.
In the embodiment of the present invention, the voltage applied may be 1-200V, such as 20V, 50V, 100V, 200V, etc., preferably 60V, and the voltage is applied for 0.1-10s, such as 0.1s, 1s, 5s, etc., preferably 0.5s-1s, so that the temperature between the electrodes reaches about 2000-2500 ℃. The distance between the two contact electrodes also has an influence when a voltage is applied, and is 1cm to 20 cm, for example, 1cm, 4cm, 10cm, and preferably 5cm to 10 cm. Insufficient temperature or non-uniform temperature may be caused by factors such as too low voltage, too short electrode distance, and too short voltage application time. It should be noted that, according to the actual requirement, the apparatus can also realize intermittent pulse heating of the prepared material, for example, while the rotating traction component 106 is used for traction of the conductive substrate 107, a pulse voltage with a certain frequency is applied to the conductive substrate 107 between the contact electrodes 105, the single power-on time is 0.1-10s, such as 0.1s, 1s, 5s and the like, preferably 0.5s-1s, and the direct current pulse frequency is 0.1-20Hz, such as 0.1Hz, 0.5Hz, 1Hz and the like, preferably 0.5 Hz.
It should be noted that, for the parts of the method embodiments that are not described in detail, reference is made to the device embodiments, and details are not repeated here.
In order to describe the apparatus and method for continuously synthesizing powder material based on thermal shock in more detail, the following examples are provided for further explanation. It should be noted that the embodiments of the present invention provide examples and illustrate the application of the embodiments to the preparation of alloy nanoparticle catalysts or sintered oxide powders. It will be readily appreciated by those skilled in the art that various modifications, additions, substitutions, deletions, or other changes may be made to the embodiments described below in order to apply the inventive concepts described herein to other types of composite or supported powder materials, sintered materials, high temperature heat treated materials, and still fall within the scope of the principles of the devices set forth herein.
Example 1
Firstly, the carbon fiber cloth is installed on the device in a mode of figure 3, a contact electrode structure shown in figure 5 is used, argon gas is introduced into a cavity 101, voltage with the frequency of 0.5Hz, the pulse width of 0.2s and the voltage of 30V is applied to two ends of the fiber, and a traction assembly 106 at two ends is started to keep the rotating speed of 0.5 cm/s. The distance between the contact electrodes 105 was 4cm, and each section of the material to be heated received about 4 thermal shocks.
Then, an ethanol solution of a precursor chloride for synthesizing the alloy nanomaterial is dropped on the carbon fiber cloth. Specifically, the solution comprises palladium chloride, ruthenium chloride, cobalt chloride, copper chloride, nickel chloride and ferric chloride which are respectively 0.01mol/L, and 200 microliter of precursor solution is dripped into each square centimeter of carbon fiber cloth. After drying, the carbon fiber cloth carrying the precursor salt is pulled into a heating zone. The heating zone receives a voltage pulse having a temperature peak at about 2500 ℃.
And finally, collecting the carbon fiber cloth carrying the metal salt after thermal shock treatment to obtain the carbon material carrying the alloy nanoparticles.
FIG. 10 schematically shows an SEM image of the alloy nanoparticles synthesized in example 1, and shows the uniformly distributed alloy nanoparticles having a particle size of about 100-200 nm. Fig. 11 schematically shows an EDX mapping chart of the alloy nanoparticles synthesized in example 1, which can be seen as pdrucconicufe alloy nanoparticles with uniform element distribution.
Example 2
Firstly, the carbon paper is installed on the device in a mode shown in fig. 4, a contact electrode structure shown in fig. 8 is used, argon gas is introduced into a cavity 101, voltage with the frequency of 0.1Hz, the pulse width of 8s and the voltage of 30V are applied to two ends of the fiber, a two-end traction assembly 106 is started, a group of materials to be heated are pulled every ten seconds to enter a heating area, then traction is stopped, and the materials to be heated receive static thermal shock in the heating area. The distance between the electrodes is 4cm, and each section of the material to be heated only receives 1 time of thermal shock.
Then, the oxide powder for thermal shock sintering is pressed, sandwiched between the two-layer conductive substrates 107. Specifically, zirconium oxide and yttrium oxide in a ratio of 20: 1 are uniformly ground, then are subjected to compression molding under a static pressure of 20MPa, and are sandwiched between conductive substrates before a heating zone. Subsequently, the conductive substrate 107, carrying the oxide to be sintered, is drawn into a heating zone, which receives a voltage pulse with a temperature peak of about 2000 ℃.
And finally, taking out the oxide ceramic after the thermal shock sintered oxide leaves the heating area.
Fig. 12 schematically shows an SEM image of the sintered oxide ceramic of example 2, and it can be seen that the ceramic body is dense. The obtained oxide ceramic has less cracks and high strength.
In summary, embodiments of the present invention provide an apparatus and a method for continuously synthesizing a powder material based on thermal shock, in which a conductive substrate capable of being connected to a contact electrode in a movable surface contact manner is disposed in a cavity to carry a precursor of a material to be heat-treated, and the conductive substrate is pulled to move along the contact electrode, so that the precursor of the material to be heat-treated continuously or intermittently passes through a heating section in a preset atmosphere, and the heating section continuously or intermittently performs electrothermal shock to allow the conductive substrate and the precursor of the material carried by the conductive substrate to undergo continuous rapid temperature rise, high temperature heat treatment and rapid annealing, thereby effectively avoiding tedious device assembly and thermal shock preparation with extremely low time efficiency under strict thermal shock conditions, and realizing rapid pipeline preparation of a thermal shock synthesized nano material. The method for preparing the thermal shock nano material has the advantages of high yield, stable batch quality, simple operation and low equipment requirement.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An apparatus for continuously synthesizing powder material based on thermal shock, comprising:
the device comprises a cavity (101), wherein the wall of the cavity (101) is provided with an inlet port (102) and an outlet port (103), and a contact electrode (105) is arranged inside the cavity;
the conductive substrate (107) is in movable surface contact connection with the contact electrode (105), and the conductive substrate (107) penetrates through the inlet and outlet port (102), wherein the conductive substrate (107) is used for carrying a precursor of a material to be thermally treated, and the material to be thermally treated comprises a powder material and a supported powder material;
a pulling assembly (106), wherein the pulling assembly (106) is connected with the conductive substrate (107) to pull the conductive substrate (107) to move continuously or intermittently in the cavity (101);
and the lead (104) is connected with the contact electrode (105) and an external power supply, and the lead (104), the contact electrode (105), the external power supply and the conductive substrate (107) form a closed loop.
2. The device according to claim 1, wherein a recess is provided on the contact electrode (105) and the pulling assembly (106), the electrically conductive substrate (107) being placed in the recess.
3. The device according to claim 1, wherein the conductive substrate (107) is a single layer conductive substrate or a double layer conductive substrate or a multilayer conductive substrate.
4. The device according to any one of claims 1-3, wherein the material of the electrically conductive substrate (107) comprises:
at least one of carbon cloth, carbon paper, carbon fiber, pressed carbon felt, carbon fiber film and tungsten foil;
or compounding at least one of the carbon cloth, the carbon paper, the carbon fiber, the pressed carbon felt, the carbon fiber film and the tungsten foil with the high-temperature-resistant insulating substrate;
the material to be heat-treated comprises at least one of carbon black, activated carbon, titanium oxide, tungsten oxide, aluminum oxide, silicon oxide, cerium oxide, cuprous oxide, zeolite, carbon nitride, tantalum nitride, titanium nitride, gallium nitride, cobalt phosphide and iron nickel phosphide.
5. A device according to any of claims 1-3, wherein the electrically conductive substrate (107) has a width in the range of 5-100mm, a thickness in the range of 0.1-4mm and an electrical conductivity in the range of 1-1000m Ω/cm.
6. The device according to claim 1, wherein the contact electrode (105) comprises an electrode sheet or an electrode bar or a brush or an electrode clamp or an electrode sheet or a metal pulley or a graphite pulley, and the contact electrode (105) is in continuous direct contact with the conductive substrate (107) or intermittently clamps the conductive substrate (107) in an intermittent opening and closing manner during the movement of the conductive substrate (107).
7. The device of claim 1, wherein the external power source is a dc power source, rated voltage ranges from 1 to 200V, rated current ranges from 1 to 50A, and dc pulse frequency ranges from 0.1 to 20 Hz.
8. A method for synthesizing nanomaterial based on the apparatus for synthesizing nanomaterial based on thermal shock of any one of claims 1 to 7, comprising:
carrying a precursor of the material to be heat-treated on the conductive substrate (107);
drawing the conductive substrate (107) to move along the contact electrode (105) to make the precursor of the material to be heat-treated continuously or intermittently pass through a heating section under a preset atmosphere.
9. The method of claim 8, wherein the heating section employs a continuous heating mode or a batch heating mode;
the preset atmosphere comprises nitrogen, argon, hydrogen or carbon dioxide or a local atmosphere generated when an additive for thermal reaction added in a precursor of the material to be thermally treated is thermally decomposed or gasified, wherein the additive comprises at least one of elemental boron, elemental phosphorus, elemental sulfur, urea, melamine, or vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten, silver, gold, ruthenium, rhodium, palladium, iridium, platinum, gallium and indium, chloride salt, nitrate, acetate or acetylacetone salt.
10. The method according to claim 9, wherein the electrically conductive substrate (107) has a pulling speed of 0.1-10cm/s and a single energization heating time of 0.1-10 s.
CN202011160025.XA 2020-10-23 2020-10-23 Device and method for continuously synthesizing powder material based on thermal shock Pending CN112404449A (en)

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