CN113023687B - Method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology - Google Patents
Method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology Download PDFInfo
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- CN113023687B CN113023687B CN202110241533.9A CN202110241533A CN113023687B CN 113023687 B CN113023687 B CN 113023687B CN 202110241533 A CN202110241533 A CN 202110241533A CN 113023687 B CN113023687 B CN 113023687B
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- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 30
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000005516 engineering process Methods 0.000 title claims abstract description 16
- 238000002490 spark plasma sintering Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 7
- 229910001285 shape-memory alloy Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 239000011218 binary composite Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000003756 stirring Methods 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000002829 reductive effect Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 229910016312 BiSb Inorganic materials 0.000 description 1
- 229910016339 Bi—Sb—Te Inorganic materials 0.000 description 1
- 229910017629 Sb2Te3 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of nano bismuth antimony tellurium based on a spark plasma sintering technology, belonging to the field of nano material preparation, and the scheme is that a lower bearing mould and an upper closed mould are matched to promote a movable inserted bar to be extruded so as to push the movable inserted bar to move upwards along a through hole, under the action of the airflow exchange holes, the air remained in the sintering groove enters the built-in cavity, and by means of the reaction of the reducing iron powder and the air, on one hand, a large amount of heat can be generated, thereby improving the sintering effect in the preparation process, reducing the possibility of oxidation of the composite material in the reaction process by virtue of the effect on air, and on the other hand, by virtue of the upward movement of the upper connecting disc, the elastic thin rod can be driven to fully stir and disperse the reducing iron powder, so that the reaction effect of the reducing iron powder and air is improved.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a method for preparing nano bismuth, antimony and tellurium based on a spark plasma sintering technology.
Background
The Spark Plasma Sintering (SPS) process is a new powder metallurgy Sintering technology which is characterized in that metal powder and the like are filled into a die made of graphite and the like, a specific Sintering power supply and pressing pressure are applied to the sintered powder by utilizing an upper die punch, a lower die punch and a power-on electrode, and a high-performance material is prepared through discharge activation, thermoplastic deformation and cooling.
Bismuth antimony tellurium (Bi-Sb-Te) -based thermoelectric materials, such as Bi2Te3, Sb2Te3, and BiSb and other group V-VI semiconductor compounds, are one of the important materials currently used in low-temperature thermoelectric devices, and are also one of the oldest thermoelectric materials under study, and have a large Seebeck coefficient and a low thermal conductivity, for example, under the condition of 300K at room temperature, the thermoelectric figure of merit of an alloy bi0.5sb1.5te3 is about 1, and the corresponding conversion efficiency exceeds 7%, and most of the commercial refrigeration components currently adopt such materials.
In the prior art, in the process of preparing the nano-scale bismuth antimony tellurium, the discharge plasma sintering technology is generally adopted, but in the actual preparation process, part of the bismuth antimony tellurium can be oxidized due to the high temperature during sintering, so that the purity of the nano-scale bismuth antimony tellurium is reduced.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a method for preparing nano bismuth antimony tellurium based on a spark plasma sintering technology, the scheme is that a lower bearing mould and an upper closed mould are matched to promote a movable insertion rod to be extruded, so that the movable insertion rod is pushed to move upwards along a through hole, under the action of an airflow exchange hole, air remained in a sintering groove enters a built-in cavity, and by virtue of the reaction of reducing iron powder and air, on one hand, a large amount of heat can be generated, so that the sintering effect in the preparation process is improved, and by virtue of the effect on air, the possibility that a composite material is oxidized in the reaction process can be reduced, and on the other hand, by virtue of the upwards movement of an upper connecting disc, an elastic thin rod can be driven to fully stir the reducing iron powder, so that the reaction effect of the reducing iron powder and the air is improved.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A preparation method of nano bismuth antimony tellurium based on spark plasma sintering technology comprises the following steps:
s1, selecting a certain amount of Sb, Bi and Te elementary substance targets as materials, cutting the materials respectively, and forming Sb/Te and Bi/Te composite materials with a certain area ratio according to the required element ratio;
s2, placing the composite material into an ultrasonic solution, carrying out ultrasonic cleaning on the substrate by using the organic solution, pretreating the substrate by using an auxiliary ion source with the plasma energy lower than 0.8KeV, and respectively pretreating the surfaces of the Sb/Te and Bi/Te binary composite target materials by using a main sputtering ion source with the plasma energy lower than 1 KeV;
and S3, crushing the treated composite material, putting the crushed composite material into a graphene mold containing a through electrode, and electrifying to finish the preparation of the nano bismuth antimony tellurium.
Further, the graphene mold in S3 includes a lower bearing mold and an upper closed mold, the lower bearing mold has a sintering groove drilled at an upper end thereof, the upper closed mold has a built-in cavity drilled therein, the upper closed mold has a plurality of through holes uniformly distributed at a bottom end thereof, a movable plunger is inserted into the through holes, the movable plunger has a plurality of airflow exchanging holes uniformly distributed therein, an upper connecting disc located in the built-in cavity is connected to an upper end of the movable plunger, a return spring is connected between the upper connecting disc and an inner wall of the built-in cavity, an elastic thin rod is connected between two adjacent upper connecting discs, the movable plunger is pressed by closing the lower bearing mold and the upper closed mold, so that the movable plunger is pushed to move up along the through holes, and air remaining in the sintering groove enters the built-in cavity under the action of the airflow exchanging holes, with the help of the reaction of reducing iron powder and air, can produce a large amount of heats on the one hand to improve the sintering effect in the preparation process, and with the help of the effect to the air, can reduce at the in-process of reaction, the possibility that combined material is oxidized, on the other hand shifts up with the help of connecting the disc, can drive the elasticity pin and fully stir reducing iron powder and scatter, thereby improves the reaction effect of reducing iron powder and air.
Further, built-in cavity inner wall is connected with a plurality of evenly distributed's pneumatic sleeve, the thin pole of elasticity runs through pneumatic sleeve, pneumatic sleeve interpolation is equipped with vertical movable rod, vertical movable rod bottom is connected with the piston disc that is located pneumatic sleeve, pneumatic sleeve inner wall is connected with the connection gasbag membrane that is located piston disc downside, be connected with the heat altered rope between vertical movable rod upper end and the built-in cavity inner wall, with the help of the removal of the thin pole of elasticity, can drive vertical movable rod and shift up to make piston disc and be connected the atmospheric pressure between the gasbag membrane and reduce, and under the effect of atmospheric pressure, make to connect the gasbag membrane and take in pneumatic sleeve, with this improvement to the effect of scattering of reducing iron powder, thereby further the body changes the reaction efficiency of reducing iron powder and air.
Furthermore, the upper end of the upper closed die is provided with an adding hole in a chiseled mode, the adding hole is connected with a sealing plug in a threaded mode, and the adding hole and the sealing plug are arranged, so that technicians can conveniently add and replace the reducing iron powder in the built-in cavity at regular intervals.
Furthermore, the built-in cavity is filled with reducing iron powder, and the reducing iron powder and air can be prompted to react with each other by the aid of the reducing iron powder, so that a large amount of heat is generated.
Furthermore, the outer end of the elastic thin rod is connected with a plurality of capillary fiber spines which are uniformly distributed, the distance between every two adjacent capillary fiber spines is 0.5 mm, and the capillary fiber spines are arranged, so that when the elastic thin rod is bent, the capillary fiber spines mutually split, and the stirring effect of the elastic thin rod on the reducing iron powder is improved.
Furthermore, pneumatic sleeve pipe inner wall is connected with two pairs of stoppers, and two pairs of stoppers are located both sides about the piston disc respectively, through setting up the stopper, can reduce the possibility that appears alternate segregation between piston disc and the pneumatic sleeve pipe.
Furthermore, the bottom end of the connecting air bag membrane is connected with a traction rope, the bottom end of the traction rope is connected with an adsorption iron ball, and the adsorption iron ball can be promoted to absorb ferroferric oxide powder generated after the reductive iron powder reacts with air by arranging the traction rope and the adsorption iron ball.
Furthermore, the heat-variable guide rope is made of a nickel-titanium memory alloy material, the balance temperature of the heat-variable guide rope is 40 ℃, and the heat-variable guide rope is made of the nickel-titanium memory alloy material, so that the heat-variable guide rope can be promoted to be contracted after the temperature of the heat-variable guide rope is increased to a high-temperature phase state, and the piston disc is not easy to move downwards.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) this scheme is through bearing mould and last closed mould compound die down, can make the activity inserted bar receive the extrusion, thereby promote the activity inserted bar and move up along the through-hole, under the effect in air current exchange hole, make remaining air in the sintering groove enter into to built-in cavity, with the help of the reaction of reducing iron powder and air, can produce a large amount of heats on the one hand, thereby improve the sintering effect in the preparation process, and with the help of the effect to the air, can reduce the in-process that is being reacted, combined material is by the possibility of oxidation, on the other hand is with the help of last the shifting up of connecting the disc, can drive the thin pole of elasticity and fully stir reducing iron powder and scatter, thereby improve the reaction effect of reducing iron powder and air.
(2) Built-in cavity inner wall is connected with a plurality of evenly distributed's pneumatic sleeve, the thin pole of elasticity runs through pneumatic sleeve, pneumatic sleeve interpolation is equipped with vertical movable rod, vertical movable rod bottom is connected with the piston disc that is located pneumatic sleeve, pneumatic sleeve inner wall is connected with the connection gasbag membrane that is located piston disc downside, be connected with the heat altered rope guide between vertical movable rod upper end and the built-in cavity inner wall, with the help of the removal of the thin pole of elasticity, can drive vertical movable rod and shift up, thereby make piston disc and be connected the atmospheric pressure between the gasbag membrane and reduce, and under the effect of atmospheric pressure, make and connect the pneumatic cover of gasbag membrane income intraductal, with this improvement to the effect of scattering of reductive iron powder, thereby further improve the reaction efficiency of reductive iron powder and air.
(3) Go up to seal the mould upper end and open the chisel and have the interpolation hole, add downthehole threaded connection and have the sealing plug, through setting up interpolation hole and sealing plug, can make things convenient for the regular interpolation of technical staff and change the reducing iron powder in the built-in cavity.
(4) The built-in cavity is filled with the reducing iron powder, and the reducing iron powder and the air can be prompted to react with each other by the aid of the reducing iron powder, so that a large amount of heat is generated.
(5) The outer end of the elastic thin rod is connected with a plurality of capillary fiber spines which are uniformly distributed, the distance between every two adjacent capillary fiber spines is 0.5 mm, and when the elastic thin rod is bent, the capillary fiber spines are mutually unfolded, so that the stirring effect of the elastic thin rod on the reducing iron powder is improved.
(6) Pneumatic sleeve pipe inner wall is connected with two pairs of stoppers, and two pairs of stoppers are located both sides about the piston disc respectively, through setting up the stopper, can reduce the possibility that alternate segregation appears between piston disc and the pneumatic sleeve pipe.
(7) The bottom end of the connecting air bag membrane is connected with a traction rope, the bottom end of the traction rope is connected with an adsorption iron ball, and the adsorption iron ball can be promoted to absorb ferroferric oxide powder generated after reductive iron powder reacts with air by arranging the traction rope and the adsorption iron ball.
(8) The heat-variable guide rope is made of a nickel-titanium memory alloy material, the balance temperature of the heat-variable guide rope is 40 ℃, and the heat-variable guide rope is made of the nickel-titanium memory alloy material, so that the temperature of the heat-variable guide rope can be promoted to rise to a high-temperature phase state and then contract, and the piston disc is not easy to move downwards.
Drawings
FIG. 1 is a flow chart of the present invention;
fig. 2 is a cross-sectional view of a graphene mold section of the present invention;
FIG. 3 is a schematic view of the structure at A in FIG. 2;
FIG. 4 is a cross-sectional view of a pneumatic sleeve portion of the present invention;
FIG. 5 is a cross-sectional view of the portion of the pneumatic sleeve of the present invention after the piston disc has been moved upward.
The reference numbers in the figures illustrate:
the device comprises a lower bearing die 1, an upper sealing die 2, a 201 sealing plug, a 3 sintering groove, a 4 built-in cavity, 401 reducing iron powder, 5 through holes, 6 movable inserted rods, 7 airflow exchange holes, 8 upper connecting discs, 9 reset springs, 10 elastic thin rods, 1001 capillary fiber spines, 11 pneumatic sleeves, 12 vertical movable rods, 13 piston discs, 14 connecting airbag membranes, 1401 traction ropes, 1402 adsorption iron balls and 15 thermal change guide ropes.
Detailed Description
The drawings in the embodiments of the invention will be incorporated below; the technical scheme in the embodiment of the invention is clearly and completely described; obviously; the described embodiments are only some of the embodiments of the invention; but not all embodiments, are based on the embodiments of the invention; all other embodiments obtained by a person skilled in the art without making any inventive step; all fall within the scope of protection of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "top/bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "sleeved/connected," "connected," and the like are to be construed broadly, e.g., "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in a specific case to those of ordinary skill in the art.
Example 1:
referring to fig. 1, a method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology includes the following steps:
s1, selecting a certain amount of Sb, Bi and Te elementary substance targets as materials, cutting the materials respectively, and forming Sb/Te and Bi/Te composite materials with a certain area ratio according to the required element ratio;
s2, placing the composite material into an ultrasonic solution, carrying out ultrasonic cleaning on the substrate by using the organic solution, pretreating the substrate by using an auxiliary ion source with the plasma energy lower than 0.8KeV, and respectively pretreating the surfaces of the Sb/Te and Bi/Te binary composite target materials by using a main sputtering ion source with the plasma energy lower than 1 KeV;
and S3, crushing the treated composite material, putting the crushed composite material into a graphene mold containing a through electrode, and electrifying to finish the preparation of the nano bismuth antimony tellurium.
Referring to fig. 2-3, the graphene mold in S3 includes a lower supporting mold 1 and an upper sealing mold 2, a sintering groove 3 is cut at the upper end of the lower supporting mold 1, a built-in cavity 4 is cut in the upper sealing mold 2, a plurality of through holes 5 are cut at the bottom end of the upper sealing mold 2 and are uniformly distributed, a movable plunger 6 is inserted in the through holes 5, a plurality of airflow exchanging holes 7 are cut in the movable plunger 6 and are uniformly distributed, an upper connecting disc 8 located in the built-in cavity 4 is connected to the upper end of the movable plunger 6, a return spring 9 is connected between the upper connecting disc 8 and the inner wall of the built-in cavity 4, an elastic thin rod 10 is connected between two adjacent upper connecting discs 8, the movable plunger 6 can be extruded by closing the lower supporting mold 1 and the upper sealing mold 2, so as to push the movable plunger 6 to move up along the through holes 5, and under the action of the airflow exchanging holes 7, make remaining air in the sintering groove 3 get into to built-in cavity 4 in, with the help of the reaction of reducing iron powder 401 with the air, can produce a large amount of heats on the one hand, thereby improve the sintering effect in the preparation process, and with the help of the effect to the air, can reduce at the in-process of reaction, the possibility that combined material is oxidized, on the other hand shifts up with the help of connecting disc 8, can drive elasticity pin 10 and fully stir reducing iron powder 401 and scatter, thereby improve the reaction effect of reducing iron powder 401 and air.
Referring to fig. 4-5, the inner wall of the built-in cavity 4 is connected with a plurality of pneumatic sleeves 11 which are uniformly distributed, an elastic thin rod 10 penetrates through the pneumatic sleeves 11, a vertical movable rod 12 is inserted into the pneumatic sleeves 11, the bottom end of the vertical movable rod 12 is connected with a piston disc 13 which is positioned in the pneumatic sleeves 11, the inner wall of the pneumatic sleeves 11 is connected with a connecting airbag film 14 which is positioned at the lower side of the piston disc 13, a thermal change guide rope 15 is connected between the upper end of the vertical movable rod 12 and the inner wall of the built-in cavity 4, the vertical movable rod 12 can be driven to move upwards by the movement of the elastic thin rod 10, thereby causing the air pressure between the piston disc 13 and the connecting air bag membrane 14 to decrease, and under the action of the atmospheric pressure, causing the connecting air bag membrane 14 to be retracted into the pneumatic sleeve 11, thereby improving the stirring effect on the reducing iron powder 401 and further improving the reaction efficiency of the reducing iron powder 401 and the air.
Referring to fig. 2, an adding hole is drilled in the upper end of the upper closed mold 2, a sealing plug 201 is connected to the adding hole through a thread, a technician can conveniently add and replace the reducing iron powder 401 in the built-in cavity 4 at regular intervals by arranging the adding hole and the sealing plug 201, the built-in cavity 4 is filled with the reducing iron powder 401, and the reducing iron powder 401 and air can be prompted to react with each other by arranging the reducing iron powder 401, so that a large amount of heat is generated.
Referring to fig. 3-4, the outer end of the elastic thin rod 10 is connected with a plurality of capillary fiber spines 1001 which are uniformly distributed, the distance between every two adjacent capillary fiber spines 1001 is 0.5 mm, the capillary fiber spines 1001 are arranged to enable the elastic thin rod 10 to bend, the capillary fiber spines 1001 are split mutually, accordingly, the stirring effect of the elastic thin rod 10 on the reducing iron powder 401 is improved, the inner wall of the pneumatic sleeve 11 is connected with two pairs of limiting blocks, the two pairs of limiting blocks are respectively located on the upper side and the lower side of the piston disc 13, and the possibility of mutual separation between the piston disc 13 and the pneumatic sleeve 11 can be reduced by arranging the limiting blocks.
Referring to fig. 4-5, the bottom end of the connecting airbag membrane 14 is connected with a pulling rope 1401, the bottom end of the pulling rope 1401 is connected with an adsorption iron ball 1402, the adsorption iron ball 1402 is enabled to absorb ferroferric oxide powder generated after the reductive iron powder 401 reacts with air by arranging the pulling rope 1401 and the adsorption iron ball 1402, the thermal change guide rope 15 is made of a nickel-titanium memory alloy material, the balance temperature of the thermal change guide rope 15 is 40 ℃, and the thermal change guide rope 15 is made of the nickel-titanium memory alloy material, so that the temperature of the thermal change guide rope 15 is increased to a high-temperature phase state and then is contracted, and the piston disc 13 is not easy to move downwards.
The above; but are merely preferred embodiments of the invention; the scope of the invention is not limited thereto; any person skilled in the art is within the technical scope of the present disclosure; the technical scheme and the improved concept of the invention are equally replaced or changed; are intended to be covered by the scope of the present invention.
Claims (7)
1. A method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology is characterized by comprising the following steps: the method comprises the following steps:
s1, selecting a certain amount of Sb, Bi and Te elementary substance targets as materials, cutting the materials respectively, and forming Sb/Te and Bi/Te composite materials with a certain area ratio according to the required element ratio;
s2, placing the composite material into an ultrasonic solution, carrying out ultrasonic cleaning on the substrate by using the organic solution, pretreating the substrate by using an auxiliary ion source with the plasma energy lower than 0.8KeV, and respectively carrying out surface pretreatment on the Sb/Te and Bi/Te binary composite target materials by using a main sputtering ion source with the plasma energy lower than 1 KeV;
s3, crushing the treated composite material, putting the crushed composite material into a graphene mold containing a through electrode, and electrifying to complete the preparation of the nano bismuth antimony tellurium;
wherein the graphene mold in S3 comprises a lower bearing mold (1) and an upper closed mold (2), the upper end of the lower bearing die (1) is provided with a sintering groove (3), the inner opening of the upper closed die (2) is provided with a built-in cavity (4), the built-in cavity (4) is filled with reducing iron powder (401), the bottom end of the upper closed die (2) is provided with a plurality of uniformly distributed through holes (5), a movable inserted bar (6) is inserted in the through hole (5), a plurality of airflow exchange holes (7) which are uniformly distributed are drilled in the movable inserted bar (6), the upper end of the movable inserted link (6) is connected with an upper connecting disc (8) positioned in the built-in cavity (4), and a return spring (9) is connected between the upper connecting disc (8) and the inner wall of the built-in cavity (4), and an elastic thin rod (10) is connected between every two adjacent upper connecting discs (8).
2. The method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology as claimed in claim 1, wherein the method comprises the following steps: built-in cavity (4) inner wall connection has a plurality of evenly distributed's pneumatic sleeve pipe (11), pneumatic sleeve pipe (11) are run through to elasticity pin (10), pneumatic sleeve pipe (11) interpolation is equipped with vertical movable rod (12), vertical movable rod (12) bottom is connected with piston disc (13) that are located pneumatic sleeve pipe (11), pneumatic sleeve pipe (11) inner wall connection has connection gasbag membrane (14) that are located piston disc (13) downside, be connected with heat altered conductor rope (15) between vertical movable rod (12) upper end and built-in cavity (4) inner wall.
3. The method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology as claimed in claim 1, wherein the method comprises the following steps: an adding hole is drilled in the upper end of the upper sealing die (2), and a sealing plug (201) is connected to the inner thread of the adding hole.
4. The method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology as claimed in claim 1, wherein the method comprises the following steps: the outer end of the elastic slender rod (10) is connected with a plurality of capillary fiber spines (1001) which are uniformly distributed, and the distance between every two adjacent capillary fiber spines (1001) is 0.5 mm.
5. The method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology as claimed in claim 2, wherein: the inner wall of the pneumatic sleeve (11) is connected with two pairs of limiting blocks, and the two pairs of limiting blocks are respectively positioned on the upper side and the lower side of the piston disc (13).
6. The method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology as claimed in claim 2, wherein the method comprises the following steps: the bottom end of the connecting air bag membrane (14) is connected with a pull rope (1401), and the bottom end of the pull rope (1401) is connected with an adsorption iron ball (1402).
7. The method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology as claimed in claim 2, wherein: the heat-variable guide rope (15) is made of a nickel-titanium memory alloy material, and the equilibrium temperature of the heat-variable guide rope (15) is 40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110241533.9A CN113023687B (en) | 2021-03-04 | 2021-03-04 | Method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology |
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