CN114835491A - Conductive ceramic material and preparation method thereof, and conductive ceramic body and preparation method thereof - Google Patents
Conductive ceramic material and preparation method thereof, and conductive ceramic body and preparation method thereof Download PDFInfo
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Abstract
The application provides a conductive ceramic material and a preparation method thereof, and a conductive ceramic body and a preparation method thereof. The preparation method of the conductive ceramic material comprises the following steps: mixing and grinding a La-containing compound, a Sr-containing compound, a Mn-containing compound and an additive according to a weight ratio to prepare slurry, wherein at least one of the La-containing compound, the Sr-containing compound and the Mn-containing compound contains O; sintering the slurry to obtain a conductive ceramic material; the conductive ceramic material contains La, Sr, Mn and O elements. The resistivity range of the conductive ceramic material prepared by the method is 1 multiplied by 10 ‑4 ～1×10 ‑6 Omega m, the thermal conductivity coefficient is more than 14 w/DEG C. m, and the application range and the application mode are wider.
Description
Technical Field
The invention relates to the technical field of conductive ceramic materials, in particular to a conductive ceramic material and a preparation method thereof, and a conductive ceramic body and a preparation method thereof.
Background
The conductive ceramic material has more and more extensive attention and application due to the stable high-temperature conductive performance, the uniform and faster current-carrying property, the excellent oxidation resistance, the corrosion resistance and the higher breakdown strength.
However, the conductive ceramic material prepared at present has the problems of higher resistivity and lower power density, for example, the conductive ceramic material prepared by a sputtering coating method has the problems of complex process, matching of substrates for bearing the conductive ceramic film and limited application range and mode.
Disclosure of Invention
The conductive ceramic material and the preparation method thereof, and the conductive ceramic body and the preparation method thereof can solve the problems of high resistivity, low power density and limited application range and mode of the conventional conductive ceramic material.
In order to solve the above technical problem, the first technical solution adopted by the present application is: provides a preparation method of a conductive ceramic material. The method comprises the following steps: mixing and grinding a La-containing compound, a Sr-containing compound, a Mn-containing compound and an additive according to a weight ratio to prepare slurry, wherein at least one of the La-containing compound, the Sr-containing compound and the Mn-containing compound contains O; sintering the slurry to obtain a conductive ceramic material; the conductive ceramic material comprises La, Sr, Mn and O elements.
In order to solve the above technical problem, the second technical solution adopted by the present application is: an electrically conductive ceramic material is provided. The conductive ceramic material comprises La, Sr, Mn and O elements.
In order to solve the above technical problem, the third technical solution adopted by the present application is: a method for preparing a conductive ceramic body is provided. The method comprises the following steps: obtaining a conductive ceramic material; the conductive ceramic material is prepared by the preparation method of the conductive ceramic material; granulating the conductive ceramic material to obtain granulated powder; pressing and molding the granulated powder to obtain a ceramic green body; sintering the ceramic green body at a preset temperature to obtain the conductive ceramic body, wherein the conductive ceramic body comprises La, Sr, Mn and O elements.
In order to solve the above technical problem, a fourth technical solution adopted by the present application is: provided is a conductive ceramic body, the composition of which contains La, Sr, Mn and O elements.
The preparation method of the conductive ceramic material comprises the steps of mixing and grinding a La-containing compound, a Sr-containing compound, a Mn-containing compound and an additive according to a weight ratio to prepare slurry, wherein at least one of the La-containing compound, the Sr-containing compound and the Mn-containing compound contains O; then sintering the slurry to obtain a conductive ceramic material; the conductive ceramic material comprises La, Sr, Mn and O; the resistivity range of the conductive ceramic material prepared by the method is 1 multiplied by 10 -4 ～1×10 -6 Omega.m, the thermal conductivity is more than 14 w/DEG C.m; the conductive ceramic material prepared by the method greatly reduces the resistivity of the prepared conductive ceramic material, improves the power density, does not need to be matched with a corresponding medium for use compared with the conductive ceramic material prepared by a sputtering film method, and has wider application range and mode.
Drawings
Fig. 1 is a flow chart of a method for preparing a conductive ceramic material according to an embodiment of the present disclosure;
FIG. 2 is a flow chart of a method of making a conductive ceramic body provided in accordance with an embodiment of the present application;
FIG. 3 is a sub-flowchart of step S22 in FIG. 2 according to an embodiment of the present application;
FIG. 4 shows an electrically conductive ceramic material (La) according to an embodiment of the present application 1-x Sr x MnO 3 ) Resistivity curves under different x formula systems;
fig. 5 is a crystal composition analysis XRD chart of the conductive ceramic materials obtained from the first to third set of experiments provided in an embodiment of the present application;
FIG. 6 is a graph of current-voltage characteristics I-V of a first set of conductive ceramic materials obtained from experiments provided in an embodiment of the present application;
fig. 7 is a crystal form composition analysis XRD pattern of the conductive ceramic bodies obtained from the first to third set of experiments provided in an embodiment of the present application;
FIG. 8 is a SEM image of a microstructure analysis of a first set of experimentally obtained conductive ceramic bodies provided in an embodiment of the present application;
FIG. 9 is a SEM image of microstructure analysis of a second set of experimentally obtained conductive ceramic bodies provided in accordance with an embodiment of the present application;
fig. 10 is a microstructure analysis SEM image of a third set of experimentally obtained conductive ceramic bodies provided in an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terms "first", "second" and "third" in this application are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any indication of the number of technical features indicated. Thus, a feature defined as "first," "second," or "third" may explicitly or implicitly include at least one of the feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless explicitly specifically limited otherwise. All directional indications (such as up, down, left, right, front, and rear … …) in the embodiments of the present application are only used to explain the relative positional relationship between the components, the movement, and the like in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indication is changed accordingly. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
The application provides a conductive ceramic material and a preparation method thereof, and a conductive ceramic body and a preparation method thereof 1-x Sr x MnO 3 (ii) a Wherein x is 0.25 to 0.4. The resistivity of the conductive ceramic material prepared by the method can be designed to be 1 x 10 -4 Ω·m～1×10 -6 Omega.m; specifically, the total weight of the powder can reach 1-3 x 10 -5 Omega, m; in the specific preparation process, the resistivity can be designed according to the use requirement; the conductive ceramic material has conductivity close to that of metal and power density over 2500mW/cm 2 The breaking strength can reach more than 70MPa, and the device can be used for designing parts such as resistance heating (atomizing heating and the like), electrodes, high-temperature resistance control circuits, power electronic devices, lasers and the like and other multiple purposes.
The present application will be described in detail with reference to the accompanying drawings and examples.
Referring to fig. 1, fig. 1 is a flow chart illustrating a method for preparing a conductive ceramic material according to an embodiment of the present disclosure; in this embodiment, a method for preparing a conductive ceramic material is provided, where the method specifically uses a solid-phase reaction to prepare the conductive ceramic material, and the method includes:
step S11: mixing and grinding the La-containing compound, the Sr-containing compound, the Mn-containing compound and the additive according to the weight ratio to obtain slurry.
Wherein at least one of the La-containing compound, the Sr-containing compound, and the Mn-containing compound contains O; in one embodiment, the La-containing compound, Sr-containing compound, and Mn-containing compound may each be La 2 O 3 、SrCO 3 、MnO 2 . In this embodiment, step S11 specifically includes: obtaining 46-50% by weight of La 2 O 3 18 to 22 weight percent of SrCO 3 35-37 wt% of MnO 2 Taking 0-4 wt% of additive as a raw material, adding water and ball milling beads, and then mixing and ball milling to obtain slurry; wherein the weight ratio of the raw materials to the ball milling beads to the water is 1:2: 0.8-1.2; the additive can be ZnO or Bi 2 O 3 ，MgO，TiO 2 ，Cr 2 O 3 And SiO 2 At least one or more of (a). Wherein, due to the raw material (La) 2 O 3 、SrCO 3 、MnO 2 And additives), can eliminate commonly used nitric acid non-safety raw materials, has simple process, safety and reliability, is prepared by adopting one-time chemical raw materials and directly carrying out solid-phase reaction synthesis, has low production cost and is suitable for industrial production.
Of course, in other embodiments, La may be used 2 O 3 、SrCO 3 、MnO 2 The raw materials are mixed and ground according to a molecular ratio, which is not limited in the present application.
Step S12: the slurry is sintered to obtain a conductive ceramic material.
Wherein, the conductive ceramic material comprises La, Sr, Mn and O elements; specifically, when the La-containing compound, the Sr-containing compound and the Mn-containing compound are respectively La 2 O 3 、SrCO 3 、MnO 2 When the conductive ceramic material is prepared, the component of the conductive ceramic material is specifically La 1- x Sr x MnO 3 Wherein x is 0.25 to 0.4.
Specifically, step S12 is performedThe method comprises the steps of drying slurry at 80-100 ℃, wherein the drying time can be 1-5 h; then calcining the dried slurry for 8-10 h at 900-1000 ℃ to obtain the conductive ceramic material. The resistivity range of the prepared conductive ceramic material is 1 multiplied by 10 after detection -4 Ω·m～1×10 -6 Omega.m, power density greater than 2500mW/cm 2 And the thermal conductivity coefficient is more than 14 w/DEG C.
The conductive ceramic material prepared by the method has the forbidden band width of about 3.3eV, and has the advantages of three-generation semiconductors, such as high breakdown strength, extremely fast electronic saturation drift velocity, high-temperature stability and the like; and the resistivity of the conductive ceramic material is in the range of 1 x 10 -4 ～1×10 -6 Omega.m, power density greater than 2500mW/cm 2 And the thermal conductivity coefficient is more than 14 w/DEG C. The prepared conductive ceramic material has good strength and high-temperature stability, can be used for high-temperature heating components and can reach more than 800 ℃ in common liquid use; in a common gaseous medium, temperatures up to 1200 ℃ may be used; the prepared conductive ceramic material has low resistivity and an extremely fast electron saturation drift velocity, and the heating speed can reach 20-30 ℃/S; meanwhile, the current density of the conductive ceramic material can exceed 2500mW/cm 2 So that the method can be expanded to more fields, such as medium direct heating, atomization heating and the like; in addition, the material has good resistance stability of a temperature field, and has wide prospect and wide application range in the application fields of resistance temperature control, stable power output control electronic components, electrodes, targets, laser and the like.
In the method for preparing a conductive ceramic material according to this embodiment, a La-containing compound, a Sr-containing compound, a Mn-containing compound, and an additive are mixed and ground according to a weight ratio to prepare a slurry, where at least one of the La-containing compound, the Sr-containing compound, and the Mn-containing compound contains O; then sintering the slurry to obtain a conductive ceramic material; the conductive ceramic material comprises La, Sr, Mn and O; the resistivity range of the conductive ceramic material prepared by the method is 1 multiplied by 10 -4 ～1×10 -6 Omega m, powerDensity greater than 2500mW/cm 2 The heat conductivity coefficient is more than 14 w/DEG C.m; the conductive ceramic material prepared by the method greatly reduces the resistivity of the prepared conductive ceramic material, improves the power density, does not need to be matched with a corresponding medium for use compared with the conductive ceramic material prepared by a sputtering film method, and has wider application range and mode.
In this embodiment, a conductive ceramic material is provided, which can be prepared by the above method; specifically, the conductive ceramic material comprises La, Sr, Mn and O; in one embodiment, the conductive ceramic material has a composition of La 1-x Sr x MnO 3 Wherein x is 0.25 to 0.4.
Specifically, the forbidden band width of the conductive ceramic material is about 3.3eV, and the conductive ceramic material has the advantages of three-generation semiconductors, such as high breakdown strength, extremely fast electron saturation drift velocity, high-temperature stability and the like; and the resistivity of the conductive ceramic material is in the range of 1 x 10 -4 ～1×10 -6 Omega.m, power density greater than 2500mW/cm 2 The heat conductivity coefficient is more than 14 w/DEG C.m, and the strength is more than 70 MPa; the prepared conductive ceramic material has good strength and high-temperature stability, can be used for high-temperature heating components and can reach more than 800 ℃ in common liquid use; in a common gaseous medium, temperatures up to 1200 ℃ may be used; the prepared conductive ceramic material has low resistivity and extremely fast electron saturation drift velocity, and the heating speed can reach 20-30 ℃/S; meanwhile, the current density of the conductive ceramic material can exceed 2500mW/cm 2 So that the method can be expanded to more fields, such as medium direct heating, atomization heating and the like; in addition, the material has good resistance stability of a temperature field, and has wide prospect and wide application range in the application fields of resistance temperature control, stable power output control electronic components, electrodes, targets, laser and the like. In addition, the bulk material can be fabricated and processed into a variety of shapes.
Referring to fig. 2, fig. 2 is a flow chart of a method for preparing a conductive ceramic body according to an embodiment of the present disclosure; in this embodiment, there is provided a method for preparing a conductive ceramic body, specifically including:
step S21: and obtaining the conductive ceramic material.
Specifically, the conductive ceramic material can be prepared by the preparation method of the conductive ceramic material provided in any one of the above embodiments; the specific implementation process can be referred to the related text description, and the same or similar technical effects can be achieved, which is not described herein again.
Step S22: the conductive ceramic material is granulated to obtain granulated powder.
Specifically, referring to fig. 3, fig. 3 is a sub-flowchart of step S22 in fig. 2 according to an embodiment of the present application; step S22 specifically includes:
step S221: a binder is added to the conductive ceramic material and wet milled to obtain a viscous slurry.
Specifically, after adding a conductive ceramic material, water, ball grinding beads and a binder on a ball mill, carrying out ball milling and crushing to prepare viscous slurry; wherein the mass ratio of the water to the conductive ceramic material to the ball milling beads is 2:3: 6; the addition amount of the binder accounts for 0.4-1.2% of the mass of the ceramic powder, so that the viscosity of the viscous slurry is less than 200Pa & S; specifically, the fineness of the powder processed in step S221 is controlled to be less than 1 micron, wherein the binder may be polyvinyl alcohol, synthetic resin, rubber, or the like.
Step S222: spray granulation of the viscous slurry is carried out at 250-280 ℃ to obtain granulated powder.
Specifically, the granularity of the granulated powder is 60-300 meshes.
Step S23: and pressing and forming the granulated powder to obtain the ceramic green body.
Specifically, the design and manufacture of a mold can be carried out according to a preset shape, and the granulated powder is pressed and formed in a dry pressing mode under the pressure of 60-120Mp to form a ceramic blank.
Step S24: sintering the ceramic green body at a preset temperature to obtain the conductive ceramic body.
Specifically, the ceramic body formed by pressing can be usedPlacing the ceramic body in a sintering furnace, controlling the heating rate to be 80-90 ℃/h, specifically 80 ℃/h, then carrying out heat preservation sintering at 1350-1650 ℃ for 2-3h, and finally obtaining the lanthanum strontium manganate-based conductive ceramic body after cooling; wherein the obtained conductive ceramic body comprises La, Sr, Mn and O elements; in one embodiment, the composition of the resulting conductive ceramic body is La 1-x Sr x MnO 3 Wherein x is 0.25 to 0.4.
The conductive ceramic body prepared by the method has the forbidden band width of about 3.3eV, and has the advantages of three-generation semiconductors, such as high breakdown strength, extremely fast electronic saturation drift velocity, high-temperature stability and the like; and the electrically conductive ceramic body has a resistivity in the range of 1X 10 -4 ～1×10 -6 Omega.m, power density greater than 2500mW/cm 2 The bending strength exceeds 70MPa, the heat conductivity coefficient is more than 14 w/DEG C.m, the resistivity of the material of the prepared conductive ceramic body is greatly reduced, and the power density is improved; the prepared conductive ceramic body has good strength and high-temperature stability, can be used for high-temperature heating components and can reach more than 800 ℃ in common liquid use; in a common gaseous medium, temperatures up to 1200 ℃ may be used; the prepared conductive ceramic body has low resistivity and extremely fast electron saturation drift velocity, and the heating speed can reach 20-30 ℃/S; meanwhile, the current density of the conductive ceramic body can exceed 2500mW/cm 2 So that the method can be expanded to more fields, such as medium direct heating, atomization heating and the like; in addition, the conductive ceramic body has good resistance stability of a temperature field, and also has wide prospect and wider application range in the application fields of resistance temperature control, stable power output control electronic components, electrodes, target materials, laser and the like.
Specifically, referring to fig. 4, fig. 4 is a conductive ceramic material (La) provided in an embodiment of the present application 1-x Sr x MnO 3 ) Resistivity curves under different x formula systems; the experimental result shows that the component is La 1-x Sr x MnO 3 When x is more than 0.4 and less than 0.25, the resistivity of the conductive ceramic material is rapidly increasedTherefore, the method controls x to be within the range of 0.25 to 0.4 when the conductive ceramic material is prepared, so that the resistivity of the conductive ceramic material is within the range of 1.25 multiplied by 10 -5 ～1.8×10 -5 Omega.m, thereby improving the conductivity of the conductive ceramic material.
Specifically, in the first set of experiments, 46.5g of La with a purity of 99% was weighed out 2 O 3 18.06g of SrCO with a purity of 99% 3 35.44g MnO of 91% purity 2 Pouring the mixture into a ball milling tank, taking zirconia balls as ball milling beads, wherein the weight of the ball milling beads is as follows: weight of ionized water: starting Material (La) 2 O 3 、SrCO 3 And MnO 2 ) The weight of (2): 1: 1.5; then fully grinding until the raw materials are uniformly mixed, wherein the fineness of the raw materials is below 1 micron; and then pouring the obtained slurry into a tray, placing the tray in a drying box with the temperature of 100-120 ℃ for drying, transferring the dried slurry into a corundum crucible, calcining the corundum crucible at the temperature of 1000 ℃ (the heating rate is 3 ℃/min), and preserving the heat for 2 hours to obtain the conductive ceramic material powder with uniform components.
Through detection, referring to fig. 4 to 6, fig. 5 is a crystal form composition analysis XRD chart of the conductive ceramic material obtained from the first to third set of experiments provided in an embodiment of the present application; FIG. 6 is a graph of current-voltage characteristics I-V of a first set of conductive ceramic materials obtained from experiments provided in an embodiment of the present application; as can be seen from FIG. 5, the composition of the conductive ceramic material powder is La 0.65 Sr 0.35 MnO 3 (ii) a As can be seen from FIGS. 4 and 6, the resistivity of the prepared conductive ceramic material was in the range of 1.35X 10 -5 ～1.5×10 -5 Omega m, and the power density of the conductive ceramic material is more than 2500mW/cm through detection 2 And the thermal conductivity coefficient is more than 14 w/DEG C.
Then preparing a conductive ceramic body by using the prepared conductive ceramic material powder; specifically, conducting ceramic material powder is ball milled again (the ball milling method is the same as the above), the fineness is controlled to be below 1 micron, and a polyvinyl alcohol binder, namely a PVA binder (1.2%) is added to prepare viscous slurry with the viscosity of less than 200 Pa.S; and then carrying out spray granulation, wherein the temperature of a spray inlet is controlled to be 255-260 ℃, the moisture of granulated powder is controlled to be less than 1%, and the granularity is 60-300 meshes. And then, performing dry pressing plate forming under 80MPa by adopting a hydraulic press. And (3) trimming the formed piece to obtain a ceramic blank, and firing the ceramic blank in a common piezoelectric-free furnace, wherein the firing heating rate is controlled at 80 ℃ per hour, the temperature is kept at 1520 ℃ at the highest temperature for 3 hours, and then the ceramic blank is naturally cooled along with the furnace to obtain the conductive ceramic body.
Measuring the performance of the fired conductive ceramic body material; as can be seen from FIGS. 7 and 8, the composition of the obtained conductive ceramic body was La 0.65 Sr 0.35 MnO 3 (ii) a Conductivity of 1.35X 10 -5 ～1.5×10 -5 Omega.m, power density greater than 2500mW/cm 2 The bending strength is more than 70 MPa; the heat conductivity coefficient is more than 14 w/DEG C.m; wherein, the crystal form composition analysis XRD is shown in figure 7, and the microstructure analysis SEM is shown in figure 8; fig. 7 is a crystal composition analysis XRD pattern of the conductive ceramic bodies obtained from the first to third experiments provided in an embodiment of the present application; fig. 8 is a microstructure analysis SEM image of a first set of experimental conductive ceramic bodies provided in an embodiment of the present application.
In a second set of experiments, 49.61g of La with a purity of 99% was weighed out 2 O 3 14.99g SrCO with a purity of 99% 3 35.40g of MnO of 91% purity 2 Pouring the mixture into a ball milling tank, taking zirconia balls as ball milling beads, wherein the weight of the ball milling beads is as follows: weight of ionized water: starting Material (La) 2 O 3 、SrCO 3 And MnO 2 ) The weight of (2): 1: 1.5; then fully grinding until the raw materials are uniformly mixed, wherein the fineness of the raw materials is below 1 micron; and then pouring the obtained slurry into a tray, placing the tray in a drying box with the temperature of 100-120 ℃ for drying, transferring the dried slurry into a corundum crucible, calcining the corundum crucible at the temperature of 1000 ℃ (the heating rate is 3 ℃/min), and preserving the heat for 2 hours to obtain the conductive ceramic material powder with uniform components.
Through detection, as can be seen from FIG. 5, the conductive ceramic material powder has a composition of La 0.6 Sr 0.4 MnO 2.98 (ii) a As can be seen from FIG. 4, the resistivity of the prepared conductive ceramic material is in the range of 1.65X 10 -5 ～1.8×10 -5 Omega.m, and the power density of the conductive ceramic material is more than 2500mW/cm 2 And the thermal conductivity coefficient is more than 14 w/DEG C.
Then preparing a conductive ceramic body by using the prepared conductive ceramic material powder; specifically, conducting ceramic material powder is ball milled again (the ball milling method is the same as the above), the fineness is controlled to be below 1 micron, and a polyvinyl alcohol binder, namely a PVA binder (1.2%) is added to prepare viscous slurry with the viscosity of less than 200 Pa.S; and then carrying out spray granulation, wherein the temperature of a spray inlet is controlled to be 255-260 ℃, the moisture of granulated powder is controlled to be less than 1%, and the granularity is 60-300 meshes. And then, performing dry pressing plate forming under 80MPa by adopting a hydraulic press. And (3) trimming the formed piece to obtain a ceramic blank, and firing the ceramic blank in a common piezoelectric-free furnace, wherein the firing heating rate is controlled at 80 ℃ per hour, the temperature is kept at the highest temperature of 1480 ℃ for 3 hours, and then the ceramic blank is naturally cooled along with the furnace to obtain the conductive ceramic body.
Measuring the performance of the fired conductive ceramic body material; as is clear from FIGS. 7 and 9, the composition of the obtained conductive ceramic body was La 0.6 Sr 0.4 MnO 2.98 (ii) a Conductivity of 1.65X 10 -5 ～1.8×10 -5 Omega.m, power density greater than 2500mW/cm 2 The bending strength is more than 70 MPa; the heat conductivity coefficient is more than 14 w/DEG C.m; wherein, the XRD pattern composition analysis is shown in fig. 7, the SEM pattern microstructure analysis is shown in fig. 9, and fig. 9 is the SEM pattern of the microstructure analysis of the conductive ceramic body obtained from the second set of experiments provided by the embodiment of the present application.
In a third set of experiments 43.92g of La with a purity of 99% were weighed out 2 O 3 18.37g of SrCO with a purity of 99% 3 36.05g of MnO of 91% purity 2 ，1.66gTiO 2 Pouring the mixture into a ball milling tank, taking zirconia balls as ball milling beads, wherein the weight of the ball milling beads is as follows: weight of ionized water: starting Material (La) 2 O 3 、SrCO 3 And MnO 2 ) The weight of (2): 1: 1.5; then fully grinding until the raw materials are uniformly mixed, wherein the fineness of the raw materials is below 1 micron; then pouring the obtained slurry into a tray, placing the tray in a drying box with the temperature of 100-120 ℃ for drying, transferring the dried slurry into a corundum crucible, calcining the corundum crucible at the temperature of 1000 ℃ (the heating rate is 3 ℃/min), and preserving the heat for 2 hours to obtain the conductive ceramic material powder with uniform componentsAnd (3) a body.
Through detection, as can be seen from FIG. 5, the conductive ceramic material powder has a composition of La 0.65 Sr 0.35 MnO 3 (ii) a As can be seen from FIG. 4, the resistivity of the prepared conductive ceramic material is in the range of 1.65X 10 -5 ～1.8×10 -5 Omega.m, and the power density of the conductive ceramic material is more than 2500mW/cm 2 And the thermal conductivity coefficient is more than 14 w/DEG C.
Then preparing a conductive ceramic body by using the prepared conductive ceramic material powder; specifically, conducting ceramic material powder is ball milled again (the ball milling method is the same as the above), the fineness is controlled to be below 1 micron, and a polyvinyl alcohol binder, namely a PVA binder (1.2%) is added to prepare viscous slurry with the viscosity of less than 200 Pa.S; and then carrying out spray granulation, wherein the temperature of a spray inlet is controlled to be 255-260 ℃, the moisture of granulated powder is controlled to be less than 1%, and the granularity is 60-300 meshes. And then, performing dry pressing plate forming under 80MPa by adopting a hydraulic press. And (3) trimming the formed piece to obtain a ceramic blank, and firing the ceramic blank in a common piezoelectric-free furnace, wherein the firing heating rate is controlled at 80 ℃ per hour, the temperature is kept at the highest temperature of 1480 ℃ for 3 hours, and then the ceramic blank is naturally cooled along with the furnace to obtain the conductive ceramic body.
Measuring the performance of the fired conductive ceramic body material; as is clear from FIGS. 7 and 9, the composition of the obtained conductive ceramic body was La 0.65 Sr 0.35 MnO 3 (ii) a Conductivity of 1.65X 10 -5 ～1.8×10 -5 Omega.m, power density greater than 2500mW/cm 2 The bending strength is more than 70 MPa; the heat conductivity coefficient is more than 14 w/DEG C.m; wherein, the XRD pattern composition analysis is shown in fig. 7, the SEM pattern microstructure analysis is shown in fig. 10, and fig. 10 is the SEM pattern of the microstructure analysis of the conductive ceramic body obtained by the third set of experiments provided in the embodiment of the present application.
In this embodiment, a conductive ceramic body is provided, which can be prepared by the method for preparing the conductive ceramic body; specifically, the conductive ceramic body comprises La, Sr, Mn and O elements; in one embodiment, the conductive ceramic body has a composition of La 1-x Sr x MnO 3 Wherein x ═0.25 to 0.4. Specifically, the conductive ceramic body may have a rectangular parallelepiped shape.
Specifically, the forbidden band width of the conductive ceramic body is about 3.3eV, and the conductive ceramic body has the advantages of three-generation semiconductors, such as high breakdown strength, extremely fast electron saturation drift velocity, high-temperature stability and the like; and the electrically conductive ceramic body has a resistivity in the range of 1X 10 -4 ～1×10 -6 Omega.m, power density greater than 2500mW/cm 2 The bending strength is more than 70MPa (the bending strength test can be carried out on an Instron1195 universal material testing machine made by English, the test strip used for the test is 3 multiplied by 4 multiplied by 35(mm multiplied by mm), the span is 30mm, the loading rate is 0.5 mm/min. measured by a three-point bending method, and the thermal conductivity is more than 14 w/DEG C. m; the prepared conductive ceramic body has good strength and high-temperature stability, can be used for high-temperature heating components and can reach more than 800 ℃ in common liquid use; in a common gaseous medium, temperatures up to 1200 ℃ may be used; the prepared conductive ceramic body has low resistivity and extremely fast electron saturation drift velocity, and the heating speed can reach 20-30 ℃/S; meanwhile, the current density of the conductive ceramic body can exceed 2500mW/cm 2 So that the method can be expanded to more fields, such as medium direct heating, atomization heating and the like; in addition, the conductive ceramic body has good resistance stability of a temperature field, and also has wide prospect and wider application range in the application fields of resistance temperature control, stable power output control electronic components, electrodes, target materials, laser and the like.
The above embodiments are merely examples and are not intended to limit the scope of the present disclosure, and all modifications, equivalents, and flow charts using the contents of the specification and drawings of the present disclosure or those directly or indirectly applied to other related technical fields are intended to be included in the scope of the present disclosure.
Claims (17)
1. A method of preparing an electrically conductive ceramic material, comprising:
mixing and grinding a La-containing compound, a Sr-containing compound, a Mn-containing compound and an additive according to a weight ratio to prepare slurry, wherein at least one of the La-containing compound, the Sr-containing compound and the Mn-containing compound contains O;
sintering the slurry to obtain a conductive ceramic material; the conductive ceramic material comprises La, Sr, Mn and O elements.
2. The method for preparing a conductive ceramic material according to claim 1, wherein the La-containing compound, the Sr-containing compound, and the Mn-containing compound are La, and Mn, respectively 2 O 3 、SrCO 3 、MnO 2 The conductive ceramic material comprises La 1-x Sr x MnO 3 Wherein x is 0.25 to 0.4.
3. The method for preparing a conductive ceramic material according to claim 2, wherein the additive is ZnO or Bi 2 O 3 ，MgO，TiO 2 ，Cr 2 O 3 And SiO 2 At least one or more of (a).
4. The method for preparing a conductive ceramic material according to claim 3, wherein the step of mixing and grinding the La-containing compound, the Sr-containing compound, the Mn-containing compound and the additive according to the weight ratio to prepare the slurry specifically comprises the following steps:
obtaining 46-50% by weight of La 2 O 3 18 to 22 weight percent of SrCO 3 35-37 wt% of MnO 2 And 0-4% of additive in percentage by weight as raw materials, adding water and ball milling beads, and then mixing and ball milling; wherein the weight ratio of the raw materials to the ball milling beads to the water is 1:2: 0.8-1.2.
5. The method for preparing an electrically conductive ceramic material according to claim 4, wherein the step of sintering the slurry to obtain an electrically conductive ceramic material specifically comprises:
drying the slurry at 80-100 ℃;
and calcining the dried slurry for 8 to 10 hours at the temperature of 900 to 1000 ℃ to obtain the conductive ceramic material.
6. The method for preparing a conductive ceramic material according to claim 5, wherein the resistivity of the conductive ceramic material is in the range of 1 x 10 -4 Ω·m～1×10 -6 Omega.m; the thermal conductivity is more than 14 w/DEG C.
7. An electrically conductive ceramic material, characterized in that the composition of the electrically conductive ceramic material comprises the elements La, Sr, Mn and O.
8. The electrically conductive ceramic material according to claim 7, wherein the composition of the electrically conductive ceramic material is La 1- x Sr x MnO 3 (ii) a Wherein x is 0.25 to 0.4.
9. The electrically conductive ceramic material of claim 7, wherein the electrically conductive ceramic material has a resistivity in the range of 1 x 10 -4 Ω·m～1×10 -6 Omega.m; the thermal conductivity is more than 14 w/DEG C.
10. A method of making a conductive ceramic body, comprising:
obtaining a conductive ceramic material; the conductive ceramic material is prepared by the preparation method of the conductive ceramic material according to any one of claims 1 to 5;
granulating the conductive ceramic material to obtain granulated powder;
carrying out compression molding on the granulated powder to obtain a ceramic green body;
and sintering the ceramic green body at a preset temperature to obtain the conductive ceramic body, wherein the conductive ceramic body comprises the components of La, Sr, Mn and O.
11. The method of preparing a conductive ceramic body of claim 10, wherein the conductive ceramic body is prepared byThe composition of the porcelain material is La 1-x Sr x MnO 3 (ii) a Wherein x is 0.25 to 0.4.
12. The method of preparing an electrically conductive ceramic body according to claim 10, wherein the step of granulating the electrically conductive ceramic material to obtain a granulated powder specifically comprises:
adding a binder to the conductive ceramic material and wet-milling to obtain a viscous slurry; wherein the addition amount of the binder is 0.4-1.2% of the weight of the conductive ceramic material, and the viscosity of the viscous slurry is less than 200Pa & S;
spray granulating the viscous slurry at 250-280 ℃ to obtain granulated powder.
13. The method of producing an electrically conductive ceramic body according to claim 10, wherein the pressure at which the granulated powder is press-molded is in the range of 60 to 120 MPa; the preset temperature range is 1350-1650 ℃.
14. The method of preparing a conductive ceramic body according to claim 10, wherein the conductive ceramic body has a resistivity in the range of 1 x 10 -4 Ω·m～1×10 -6 Omega.m; the thermal conductivity is more than 14 w/DEG C.
15. A conductive ceramic body characterized in that the composition of the conductive ceramic body contains La, Sr, Mn and O elements.
16. The conductive ceramic body of claim 15, wherein the composition of the conductive ceramic body is La 1- x Sr x MnO 3 (ii) a Wherein x is 0.25 to 0.4.
17. The conductive ceramic body of claim 15, wherein the conductive ceramic body is cuboid.
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