CN111057985A - High-performance perovskite type oxide powder for thermal spraying and preparation method and application thereof - Google Patents
High-performance perovskite type oxide powder for thermal spraying and preparation method and application thereof Download PDFInfo
- Publication number
- CN111057985A CN111057985A CN201911407856.XA CN201911407856A CN111057985A CN 111057985 A CN111057985 A CN 111057985A CN 201911407856 A CN201911407856 A CN 201911407856A CN 111057985 A CN111057985 A CN 111057985A
- Authority
- CN
- China
- Prior art keywords
- powder
- ball milling
- thermal spraying
- perovskite
- type oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Glanulating (AREA)
Abstract
The invention discloses high-performance perovskite oxide powder for thermal spraying and a preparation method and application thereof, relating to the technical field of functional ceramic materials, wherein the preparation method comprises the following steps: re-granulating the perovskite type oxide superfine powder with the powder particle size of 1-3 mu m, wherein the re-granulation comprises the following steps: carrying out primary ball milling mixing on the superfine powder, the solvent and the first dispersing agent to obtain first slurry, and carrying out secondary ball milling mixing on the first slurry and the binder to obtain second slurry; the second slurry is spray granulated and then calcined. The high-performance perovskite oxide powder for thermal spraying is prepared by the method, has uniform particle size distribution, high sphericity and stable performance, and is very suitable for being applied to thermal spraying.
Description
Technical Field
The invention relates to the technical field of functional ceramic materials, in particular to high-performance perovskite oxide powder for thermal spraying and a preparation method and application thereof.
Background
Perovskite type (ABO)3) Oxides are a miraculous material. Most of these oxides are non-stoichiometric compounds, with metal cations and oxygen ion defects in their structure. The perovskite structure is essentially characterized in that A cations and oxygen ions form a basically dense arrangement surface, and the combination of the A cations and the oxygen ions has an ionic bond characteristic. The change in valence state of the a cation affects the oxygen ion state, which is a direct cause of oxygen ion defects, and the interaction of the a cation with oxygen ion plays a crucial role in the evolution of the perovskite structure. An ideal perovskite structure unit cell can theoretically form 14 oxygen deficient units. The basic units are stacked together through certain symmetrical operation to form a series of new structures, and the new structures can endow the perovskite oxide with functions of catalysis, oxygen transportation, superconductivity, ferroelectricity, ferromagnetism and the like.
The most remarkable function of the perovskite oxide is that the perovskite oxide has oxygen ion and electron conductivity properties at high temperature. Based on this function, researchers first focused their attention on the energy field in the application of perovskite oxide materials. Perovskite oxide materials have been used as the primary constituent in Solid Oxide Fuel Cell (SOFCs) cathodes, which have been vigorously developed in recent years. In the research field of inorganic oxygen permeable membranes (OTMs) with wide application prospect, perovskite type oxides are continuously concerned as membrane main materials for more than thirty years.
At present, although much of SOFCs are technically mature, their commercialization and commercialization progress has been faced with high cost hurdles. The main principle for solving the problem is to realize the medium and low temperature of the operation temperature and the diversification and rapid development of the fuel and a batch preparation technology. The medium-low temperature can increase the selection range of component materials, reduce thermal stress, improve the stability of the battery and prolong the service life. The characteristic that the thermal spraying technology is used for depositing the coating rapidly and in a large area is utilized, and the coating is applied to preparing the SOFCs single cells, so that the cost is further reduced.
Although much productive work has been done on materials, configurations, and manufacturing techniques for OTMs, their industrial applications still face a number of technical obstacles, including the fact that conventional wet-chemical methods produce films that are brittle, mechanically weak, and not easily joined at high temperatures. In order to solve these problems, researchers have proposed the preparation of supported OTMs having a composite structure composed of a dense membrane layer and a porous metal support, but since the porous metal support and the membrane material cannot be co-sintered, it is difficult to prepare a metal supported membrane using the conventional method. In this situation, researchers have attempted to exploit the feature that plasma spray technology can rapidly deposit ceramic coatings on metals and use them to prepare oxygen permeable membranes. With the development of Low pressure plasma spraying-thin coating technology (LPPS-TF) and supersonic plasma spraying technology in recent years, the compactness of the oxygen permeable membrane prepared by the thermal spraying technology is also greatly improved.
It can therefore be seen that this trend towards fusing SOFCs, OTMs and thermal spray technology will be enhanced from a future point of view of commercial and industrial applications. However, in view of the current situation, commercial perovskite-type powder materials suitable for thermal spraying have problems of single type and non-outstanding performance, and therefore it is necessary to develop high-performance perovskite-type oxide powder materials and methods for preparing the same for thermal spraying technology.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide high-performance perovskite oxide powder for thermal spraying and a preparation method and application thereof.
The invention is realized by the following steps:
in a first aspect, an embodiment provides a method for preparing a high-performance perovskite oxide powder for thermal spraying, including:
re-granulating the perovskite type oxide superfine powder with the powder particle size of 1-3 mu m, wherein the re-granulation comprises the following steps: carrying out primary ball milling mixing on the superfine powder, the solvent and the first dispersing agent to obtain first slurry, and carrying out secondary ball milling mixing on the first slurry and the binder to obtain second slurry; the second slurry is spray granulated and then calcined.
In an alternative embodiment, the solvent comprises at least one of water and ethanol;
in an alternative embodiment, the water is deionized water;
in an optional embodiment, the mass ratio of the solvent to the ultrafine powder is 1.22-2.33: 1.
In an optional embodiment, the mass ratio of the ball milling medium to the superfine powder in each ball milling is 1-3: 1;
in an optional embodiment, the ball milling medium comprises zirconia balls with the particle sizes of 4-8 mm, 8-12 mm and 18-22 mm respectively;
in an alternative embodiment, the number ratio of the zirconia balls of the three particle sizes is 8:4: 1;
in an optional embodiment, the rotation speed of each ball milling is 200-400 rpm;
in an alternative embodiment, the time of each ball milling is 2-4 h.
In an optional embodiment, the mass ratio of the first dispersing agent to the binder to the ultrafine powder is 3-10: 3-12: 100;
in an alternative embodiment, the first dispersant is polyacrylic acid;
in an alternative embodiment, the binder is polyvinylpyrrolidone.
In an alternative embodiment, the process conditions for spray granulation are: the feeding speed is 50-100 ml/min, the inlet temperature is 230-300 ℃, the outlet temperature is 60-130 ℃, the pressure in the cavity is 1-2 bar, and the atomizer is adjusted to be 3-6 m3/h。
In an alternative embodiment, the temperature of calcination is 300 to 500 ℃;
preferably, the calcination heat preservation time is 4-8 h.
In an alternative embodiment, the perovskite oxide has the general structural formula:
SrCo1-xNbxO3-δwherein x is more than or equal to 0.1 and less than or equal to 0.25, delta is an oxygen vacancy, and delta is more than or equal to 0.475 and less than or equal to 0.55;
in an alternative embodiment, the perovskite oxide is synthesized by: according to the structural general formula, the preparation raw materials are as follows: SrCO3、Co3O4And Nb2O5Mixing and ball milling;
drying the mixture obtained by ball milling, and roasting at the temperature of 1000-1200 ℃;
in an optional embodiment, the synthesized perovskite type oxide is added with the preparation raw materials during ball milling, and a second dispersing agent is further included;
in an alternative embodiment, the second dispersant comprises at least one of ethanol and ethylene glycol; in an optional embodiment, the ratio of the addition amount of the second dispersing agent to the total mass of the preparation raw materials is 1.22-2.33: 1;
in an optional embodiment, the mass ratio of the ball milling medium to the preparation raw material is 1-3: 1 when the synthesized perovskite type oxide is subjected to ball milling;
in an optional embodiment, when the synthesized perovskite type oxide is subjected to ball milling, a ball milling medium is a stainless steel ball with the particle size of 4-8 μm;
in an optional embodiment, the ball milling time of the synthesized perovskite type oxide is 12-24 h during ball milling;
in an alternative embodiment, the drying is carried out under vacuum at 80-100 ℃; further preferably, the drying time is 1-2 h;
in an optional embodiment, the roasting time is 12-20 h.
In an alternative embodiment, before re-granulating the ultrafine powder, the method further comprises: carrying out superfine treatment on the original powder of the perovskite type oxide, wherein the superfine treatment comprises the following steps:
crushing the original powder in a jet mill, wherein the pressure of crushing airflow is 0.8-1.0 MPa, the feeding speed of the powder is 80-100 g/min, the height of a discharge port is 15-20mm, and the crushing times are 2-3;
preferably, the breaking gas stream is compressed air.
In a second aspect, embodiments provide a high performance perovskite oxide powder for thermal spraying, prepared using the preparation method according to any one of the preceding embodiments.
In a third aspect, the examples provide the use of a high performance perovskite oxide powder for thermal spraying as in the previous embodiments in thermal spraying.
The invention has the following beneficial effects:
the preparation method provided by the invention is simple and efficient, has no pollution, can improve the stable compounding probability of the powder and the yield of the powder, and can granulate and agglomerate the superfine powder again into micron powder suitable for thermal spraying under the condition of not changing the performance of the powder. The prepared agglomerated powder for thermal spraying has high fluidity, uniform powder particle size distribution, high sphericity and stable performance, and is very suitable for being applied to thermal spraying.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows SrCo in example 10.9Nb0.1O3-δSEM topography under the first magnification of the original powder of one-tenth phase;
FIG. 2 shows SrCo in example 10.9Nb0.1O3-δSEM topography under the second magnification of the original powder of one-phase;
FIG. 3 is a graph of the EDS analysis results of the selected region of FIG. 2;
FIG. 4 is an SEM photograph of an ultrafine powder obtained by an ultrafine treatment in example 1;
FIG. 5 is an XRD pattern of the agglomerated powder after spray granulation of example 1;
FIG. 6 is an SEM topography of the agglomerated powder prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following provides a detailed description of a high-performance perovskite oxide powder for thermal spraying, and a preparation method and application thereof.
The embodiment of the invention provides a preparation method of high-performance perovskite type oxide powder for thermal spraying, which comprises the following steps: re-granulating the perovskite type oxide superfine powder with the powder particle size of 1-3 mu m, wherein the re-granulation comprises the following steps:
carrying out primary ball milling mixing on the superfine powder, water and a dispersing agent to obtain first slurry, and carrying out secondary ball milling mixing on the first slurry and a binder to obtain second slurry;
the second slurry is spray granulated and then calcined.
In the present invention, the reason why the dispersant and the binder are mixed with the ultrafine powder at different time periods is that: the dispersant and binder cause competitive adsorption on the powder particle surface and a large increase in the viscosity of the slurry in a short time. Therefore, in order to avoid this, the dispersant is added first, and the binder is added to the slurry after the dispersant is uniformly distributed. Therefore, the use efficiency of the additive can be improved, and the viscosity of the slurry can be better controlled. In other words, the primary ball milling mainly aims at realizing the uniform and stable dispersion of the ultrafine powder, and the secondary ball milling mainly aims at realizing the uniform dispersion of the binder in the slurry of the ultrafine powder and playing a certain role in agglomeration of the powder.
The ultrafine ceramic oxide powder has large specific surface energy, is easy to agglomerate and has poor fluidity, and the powder feeding during thermal spraying is extremely unstable, so the ultrafine ceramic oxide powder cannot be directly used for spraying. Under the condition of not changing the powder performance, the method provided by the invention re-granulates and agglomerates the superfine powder into micron powder suitable for thermal spraying, thereby solving the difficulties of poor fluidity and difficult spraying of ceramic powder.
The preparation method specifically comprises the following steps:
s1, synthesizing perovskite type oxide.
The structural general formula of the perovskite oxide provided by the preferred embodiment of the invention is as follows: SrCo1-xNbxO3-δWherein x is more than or equal to 0.1 and less than or equal to 0.25, delta is an oxygen vacancy, and delta is more than or equal to 0.475 and less than or equal to 0.55.
Adding a corresponding amount of preparation raw materials into the ball mill according to the structural general formula: SrCO3、Co3O4And Nb2O5And mixing and ball-milling the second dispersing agent. The mass ratio of the ball milling medium to the preparation raw material is 1-3: 1; more preferably, the ball milling media are stainless steel grinding balls with a particle size of 4-8 μm. Ball milling is carried out for 12-24 h to ensure that all the raw materials are fully mixed to obtain a ball milling mixture. And (3) drying the ball-milled mixture for 1-2 hours at 80-100 ℃ under a vacuum condition, then placing the mixture in a muffle furnace, and roasting for 12-20 hours at 1000-1200 ℃ to obtain the perovskite oxide with the structural formula.
Preferably, the second dispersant comprises at least one of ethanol and ethylene glycol; it is further preferred that the second dispersant be added in an amount corresponding to the total mass of the starting materials (i.e., SrCO) to be prepared, in order to ensure that the starting materials are more fully dispersed in each other3、Co3O4And Nb2O5Total mass) of 1.22 to 2.33: 1.
And S2, performing superfine treatment on the original powder.
And (3) placing the perovskite type oxide raw powder prepared in the step (S1) into an airflow crusher for crushing, wherein the pressure of crushing airflow is 0.8-1.0 MPa, the powder feeding speed is 80-100 g/min, the height of a discharge hole is 15-20mm, and the crushing times are 2-3 times. And crushing to obtain the perovskite type oxide superfine powder with the particle size of 1-3 mu m.
Preferably, the breaking gas stream is compressed air.
And S3, re-granulating the superfine powder.
Mixing a solvent and the superfine powder, putting the mixture into a ball mill, adding a first dispersing agent into the ball mill, and carrying out primary ball milling and mixing for 2-4 h; and performing primary ball milling and mixing to obtain first slurry, adding a binder into the first slurry to perform secondary ball milling, wherein the ball milling time is 2-4 h to obtain second slurry.
And carrying out spray granulation on the obtained second slurry, then calcining, and screening out high-performance perovskite type oxide powder for thermal spraying with different particle size specifications according to use requirements after calcining.
The calcination temperature is 300-500 ℃, and the heat preservation time is 4-8 h. And cooling the calcined product along with the furnace to obtain the high-performance perovskite oxide powder for thermal spraying. The obtained powder is sieved to obtain thermal spraying powder with different grain size specifications.
The solvent is preferably at least one of water and ethanol. More preferably, the water used in the present invention is low cost water, and in order to avoid introducing impurities, the water is deionized water. Further preferably, in order to prepare the powder with required quality, the mass ratio of the solvent to the ultrafine powder is 1.22-2.33: 1. The ratio out of the above range may have the following problems: the powder prepared by spray drying with the ratio below is larger in granularity, and the powder formed with the ratio above is poor in agglomeration effect.
Preferably, the mass ratio of the dispersing agent to the binder to the ultrafine powder is 3-10: 3-12: 100. a mass ratio range of the dispersant below this range results in poor dispersion effect; above this range, the slurry viscosity is too high to facilitate subsequent preparation. The lower mass of binder than this range leads to undesirable agglomeration and the slurry viscosity above this range is too high for spray drying.
The dispersing agent preferably comprises polyacrylic acid and the binder preferably comprises polyvinylpyrrolidone. The reason why the dispersant is preferably polyacrylic acid is that: polyacrylic acid is relatively inexpensive and has the best dispersing effect. The binder is preferably polyvinylpyrrolidone because: some of the other binders produced powders were less effective in agglomeration than polyvinylpyrrolidone, and some were more expensive than polyvinylpyrrolidone.
In the step, zirconia balls are preferably selected as ball grinding media, and because the ultrafine powder is ceramic powder, the zirconia balls are characterized by high brittleness, high strength, high hardness, good wear resistance and stable chemical performance, the zirconia balls are selected to prolong the service life and reduce pollution.
Preferably, the milling media also includes zirconia balls of different particle sizes. The ultrafine powder is prepared into slurry and is subjected to composite ball milling by adopting ball milling balls with different sizes, so that the distribution uniformity of the ultrafine powder can be improved, and the dispersing agent and the binder can be effectively prevented from being competitively adsorbed on the surface of ultrafine particles.
Optionally, the ball milling medium may include zirconia balls having particle sizes of 4 to 8mm, 8 to 12mm, and 18 to 22mm, respectively. The number of the zirconia balls with the three particle sizes can be 8:4:1 in sequence, and can also be adjusted according to the actual use condition.
Preferably, the mass ratio of the ball milling medium to the ultrafine powder is 1-3: 1, for example, 2: 1. Too high a ball-to-material ratio can lead to low ball milling efficiency, and too low a ball-to-material ratio can lead to non-uniform and insufficient ball milling.
Preferably, in order to ensure good ball milling effect, the rotating speed of each ball milling is 200-400 rpm. The heat generated during ball milling at a speed higher than 400rpm is serious, and the performance of the slurry can be influenced; the dispersing effect is not good below 200 rpm.
The ultrafine powder slurry is subjected to spray granulation, and the advantages of rapid transfer of heat and quality in a very short time and high preparation efficiency are achieved; meanwhile, the preparation equipment is simple, the preparation temperature is low, the mass production is convenient, and the components of the powder material can be accurately controlled. The principle is as follows: the method comprises the following steps of dispersing feed liquid into fine fogdrops by using an atomizer, and quickly evaporating a solvent in a heat drying medium to form a dry powder product, wherein the method generally comprises four stages: 1, atomizing feed liquid; 2, contacting and mixing the fog group with a heat drying medium; 3, evaporating and drying the fog drops; 4 separating the dried product from the drying medium. The fine suspension is atomized into the drying chamber and heated by the hot air stream or the inner walls. During drying rapid heat and mass transfer occurs as well as evaporation of the liquid so that finally dry particles are obtained. The dried granules can be roughly classified into the following types: uniform spherical, slender spherical, pancake, circular, needle or hollow particles, and the shape and granularity of the granulated powder can be effectively controlled by adjusting the technological parameters of spray drying.
Preferably, in order to ensure better performance of the powder particles obtained by re-granulation, the process conditions of spray granulation are as follows: the feeding speed is 50-100 ml/min, the inlet temperature is 230-300 ℃, the outlet temperature is 60-130 ℃, the pressure in the cavity is 1-2 bar, and the atomizer is adjusted to be 3-6 m3/h。
Wherein, the feeding speed is mainly used for controlling the granularity of the powder after spray drying, and the excessive or insufficient granularity can cause uneven granularity distribution or larger granularity difference. The inlet and outlet temperatures mainly affect the degree of drying of the powder, but below this range, drying is insufficient, and above this range, sphericity is poor and there are many depressions. The pressure and atomizer adjustment has similar effect with the temperature adjustment, the powder prepared by spray drying in the range has better sphericity and uniform particle size distribution; outside this range, an agglomerated powder having sufficient drying and good morphology cannot be obtained.
In the invention, the original powder is prepared by the solid-phase synthesis method, then the original powder is subjected to superfine treatment, finally the superfine powder is used as a raw material, the process combining ball milling and spray granulation is adopted, and the superfine powder is uniformly distributed in the slurry in a ball milling mode to form stable dispersed powder. The ultrafine oxide powder has large specific surface energy, is easy to agglomerate and has poor fluidity, and the powder feeding during thermal spraying is extremely unstable, so the ultrafine oxide powder cannot be directly used for spraying. Under the condition of not changing the structure of the ultrafine powder, the ultrafine powder is agglomerated into micron powder suitable for thermal spraying, and the difficulties that the ceramic powder has poor fluidity and is difficult to spray are solved.
The perovskite oxide powder for thermal spraying prepared by the preparation method has the advantages of good agglomeration, high fluidity, small powder particles, uniform particle size distribution, high sphericity and stable performance.
The high-performance perovskite oxide powder for thermal spraying provided by the embodiment of the invention is prepared by the preparation method provided by the embodiment of the invention.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
According to SrCo0.9Nb0.1O3-δStoichiometric ratio of certain amount of SrCO3、Co3O4、Nb2O5Ball-milling and mixing the mixture and ethanol according to the mass ratio of 1.4:1, wherein the ball-milling medium is a stainless steel grinding ball with the particle size of 8 mu m, and the mass ratio of the ball-milling medium to the preparation raw materials is 1.5: 1. The ball milling time is 12 h; after ball milling, the mixture is put into a muffle furnace after being dried for 2h in vacuum at the temperature of 80 ℃, and is roasted for 20h at the temperature of 1000 ℃ to obtain SrCo0.9Nb0.1O3-δForming original powder.
Crushing the original powder in an airflow crusher with compressed air as airflow and pressure of 0.8MPa, feeding powder at 80g/min and discharge port height of 18mm for 2 times to obtain superfine powder of 1-3 micron size.
Mixing the ultrafine powder and deionized water according to the mass ratio of 6.5:3.5, adding the mixture into a QM-3SP4 planetary ball mill, adding polyacrylic acid and a ball milling medium into the ball mill, and carrying out ball milling for 3 hours at the rotating speed of 400rpm by using a QM-3SP4 planetary ball mill of Nanjing Nanda instruments and Co. Wherein the ball milling medium simultaneously comprises zirconia balls with the grain diameters of 6mm, 10mm and 20mm in the number ratio of 8:4: 1. The mass ratio of the polyacrylic acid to the superfine powder is 8:100, and the mass ratio of the ball milling medium to the superfine powder is 2: 1.
Mixing the first slurry with polyvinylpyrrolidone, and ball milling for 3h with a QM-3SP4 planetary ball mill of Nanda instruments of Nanjing at a rotation speed of 400rpm to obtain a second slurry. The mass ratio of the polyvinylpyrrolidone to the superfine powder is 10: 100.
In MOBILE MINORTMThe slurry obtained in the third step was granulated by spray drying in a spray dryer under the following process conditions. The process conditions are as follows: the feeding speed is 60ml/min, the inlet temperature is 280 ℃, the outlet temperature is 120 ℃, the pressure in the cavity is 1.4bar, and the atomizer is adjusted to be 5.2m3/h。
And (3) placing the powder after spray granulation into a muffle furnace, calcining for 4 hours at 450 ℃, and then cooling with the furnace and taking out to obtain final agglomerated powder, wherein the particle size of the powder is uniform and is kept within the range of 5-25 mu m. The powder is spherical, has excellent fluidity and can be directly used for preparing a coating by thermal spraying.
Example 2
According to SrCo0.9Nb0.1O3-δStoichiometric ratio of certain amount of SrCO3、Co3O4、Nb2O5Ball-milling and mixing the raw materials with ethanol according to the mass ratio of 1.3:1, wherein the ball-milling medium is a stainless steel ball with the particle size of 8 mu m, the mass ratio of the ball-milling medium to the preparation raw materials is 2:1, and the ball-milling time is 12 hours; after ball milling, the mixture is put into a muffle furnace after being dried for 2h in vacuum at the temperature of 80 ℃, and is roasted for 20h at the temperature of 1000 ℃ to obtain SrCo0.9Nb0.1O3-δForming original powder.
Crushing the original powder in a jet mill with compressed air as airflow under 0.8MPa at a powder feeding speed of 80g/min and a discharge port height of 18mm for 2 times to obtain superfine powder with a particle size of 1-3 μm.
Mixing the ultrafine powder and deionized water in a mass ratio of 6:4, adding the mixture into a QM-3SP4 planetary ball mill, adding polyacrylic acid and a ball milling medium, and carrying out ball milling for 3 hours at a rotating speed of 400rpm by using a QM-3SP4 planetary ball mill of Nanjing Nanda instruments and Co. Wherein the ball milling medium simultaneously comprises zirconia balls with the grain diameters of 6mm, 10mm and 20mm in the number ratio of 8:4: 1. The mass ratio of the polyacrylic acid to the superfine powder is 8:100, and the mass ratio of the ball milling medium to the superfine powder is 2: 1.
Mixing the first slurry with polyvinylpyrrolidone, and ball milling for 4h with a QM-3SP4 planetary ball mill of Nanda instruments of Nanjing at a rotation speed of 400rpm to obtain a second slurry. The mass ratio of the polyvinylpyrrolidone to the superfine powder is 10: 100.
In MOBILE MINORTMThe slurry obtained in the third step was granulated by spray drying in a spray dryer under the following process conditions. The process conditions are as follows: the feeding speed is 70ml/min, the inlet temperature is 280 ℃, the outlet temperature is 120 ℃, the pressure in the cavity is 1.4bar, and the atomizer is adjusted to be 4.8m3/h。
And (3) placing the powder after spray granulation into a muffle furnace, calcining for 6 hours at 350 ℃, cooling with the furnace, and taking out to obtain final agglomerated powder, wherein the particle size of the powder is uniform and is kept within the range of 15-45 mu m. The powder is spherical, has excellent fluidity and can be directly used for preparing a coating by thermal spraying.
Example 3
According to SrCo0.75Nb0.25O3-δStoichiometric ratio of certain amount of SrCO3、Co3O4、Nb2O5Ball-milling and mixing the raw materials and ethanol according to the mass ratio of 1.3:1, wherein a ball-milling medium is a stainless steel grinding ball with the particle size of 4 mu m, the mass ratio of the ball-milling medium to the prepared raw materials is 2.5:1, and the ball-milling time is 20 hours; after ball milling, the mixture is put into a muffle furnace after being dried for 2h in vacuum at the temperature of 80 ℃, and is roasted for 12h at the temperature of 1200 ℃ to obtain SrCo0.75Nb0.25O3-δForming original powder.
Crushing the original powder in a jet mill under the jet pressure of 1.0MPa, the powder feeding speed of 100g/min, the height of a discharge port of 15mm, and the crushing times of 3 times to obtain the superfine powder with the particle size of 1-3 microns.
Mixing the ultrafine powder and deionized water in a mass ratio of 6.5:3.5, adding the mixture into a QM-3SP4 planetary ball mill, adding polyacrylic acid and a ball milling medium, and ball milling for 3 hours at a rotating speed of 400rpm by using a QM-3SP4 planetary ball mill of Nanjing Nanda instruments and Co. Wherein the ball milling medium simultaneously comprises zirconia balls with the grain diameters of 6mm, 10mm and 20mm in the number ratio of 8:4: 1. The mass ratio of the polyacrylic acid to the superfine powder is 6:100, and the mass ratio of the ball milling medium to the superfine powder is 2: 1.
Mixing the first slurry with polyvinylpyrrolidone, and ball milling for 3h with a QM-3SP4 planetary ball mill of Nanda instruments of Nanjing at the rotation speed of 400rpm to obtain a second slurry. The mass ratio of the polyvinylpyrrolidone to the superfine powder is 12: 100.
In MOBILE MINORTMThe slurry obtained in the third step was granulated by spray drying in a spray dryer under the following process conditions. The process conditions are as follows: the feeding speed is 60ml/min, the inlet temperature is 280 ℃, the outlet temperature is 120 ℃, the pressure in the cavity is 1.4bar, and the atomizer is adjusted to be 4.4m3/h。
And (3) placing the powder after spray granulation into a muffle furnace, calcining for 4 hours at 450 ℃, and then cooling with the furnace and taking out to obtain final agglomerated powder, wherein the particle size of the powder is uniform and is kept within the range of 5-25 mu m. The powder is spherical, has excellent fluidity and can be directly used for preparing a coating by thermal spraying.
Example 4
According to SrCo0.75Nb0.25O3-δStoichiometric ratio of certain amount of SrCO3、Co3O4、Nb2O5Ball-milling and mixing the raw materials and ethanol according to the mass ratio of 1.4:1, wherein a ball-milling medium is a stainless steel grinding ball with the particle size of 4 mu m, the mass ratio of the ball-milling medium to the prepared raw materials is 2:1, and the ball-milling time is 20 hours; after ball milling, the mixture is put into a muffle furnace after being dried for 2h in vacuum at the temperature of 80 ℃, and is roasted for 12h at the temperature of 1200 ℃ to obtain SrCo0.75Nb0.25O3-δForming original powder.
Crushing the original powder in a jet mill under the jet pressure of 1.0MPa, the powder feeding speed of 100g/min, the height of a discharge port of 20mm, and the crushing times of 3 times to obtain the superfine powder with the particle size of 1-3 microns.
Mixing the ultrafine powder and deionized water in a mass ratio of 6.5:3.5, adding the mixture into a QM-3SP4 planetary ball mill, adding polyacrylic acid and a ball milling medium, and ball milling for 3 hours at a rotating speed of 400rpm by using a QM-3SP4 planetary ball mill of Nanjing Nanda instruments and Co. Wherein the ball milling medium simultaneously comprises zirconia balls with the grain diameters of 6mm, 10mm and 20mm in the number ratio of 8:4: 1. The mass ratio of the polyacrylic acid to the superfine powder is 6:100, and the mass ratio of the ball milling medium to the superfine powder is 2: 1.
Mixing the first slurry with polyvinylpyrrolidone, and ball milling for 3h with a QM-3SP4 planetary ball mill of Nanda instruments of Nanjing at a rotation speed of 400rpm to obtain a second slurry. The mass ratio of the polyvinylpyrrolidone to the superfine powder is 9: 100.
In MOBILE MINORTMThe slurry obtained in the third step was granulated by spray drying in a spray dryer under the following process conditions. The process conditions are as follows: the feeding speed is 60ml/min, the inlet temperature is 280 ℃, the outlet temperature is 120 ℃, the pressure in the cavity is 1.4bar, and the atomizer is adjusted to be 3.6m3/h。
And (3) placing the powder after spray granulation into a muffle furnace, calcining for 6 hours at 350 ℃, cooling with the furnace, and taking out to obtain final agglomerated powder, wherein the particle size of the powder is uniform and is kept within the range of 15-45 mu m. The powder is spherical, has excellent fluidity and can be directly used for preparing a coating by thermal spraying.
Example 5
This embodiment is substantially the same as embodiment 1 except that:
when the calcium titanium oxide is synthesized, the mass ratio of the total mass of the prepared raw materials to ethanol is 2.33:1, the ball milling time is 24 hours, the drying temperature after ball milling is 100 ℃, the drying time is 1 hour, the roasting temperature is 1100 ℃, and the roasting time is 15 hours.
Re-granulating, wherein the mass ratio of the deionized water to the superfine powder is 1.22: 1; the mass ratio of the ball milling medium to the superfine powder is 1: 1; spray granulation process with feeding speed of 50ml/min and inlet temperature of300 deg.C, outlet temperature of 130 deg.C, pressure in cavity of 1bar, and atomizer adjusted to 3m3H is used as the reference value. The calcining temperature is 300 ℃, and the holding time is 8 h.
Example 6
This embodiment is substantially the same as embodiment 1 except that:
when the calcium-titanium oxide is synthesized, the mass ratio of the total mass of the prepared raw materials to ethanol is 1.22:1, the ball milling time is 24 hours, the drying temperature after ball milling is 100 ℃, the drying time is 1 hour, the roasting temperature is 1100 ℃, and the roasting time is 15 hours.
Re-granulating, wherein the mass ratio of the deionized water to the superfine powder is 2.33: 1; the mass ratio of the ball milling medium to the superfine powder is 3: 1; spray granulating at feeding speed of 100ml/min, inlet temperature of 230 deg.C, outlet temperature of 60 deg.C, pressure in cavity of 2bar, and atomizer of 6m3H is used as the reference value. The calcining temperature is 500 ℃, and the heat preservation time is 8 h.
Experimental example 1
Taking example 1 as an example, when powder is synthesized in a solid phase, the original powder is sampled and the microscopic morphology and the original particle size of the powder particles are observed by a scanning electron microscope, and the obtained results are respectively shown in fig. 1; EDS analysis of the raw powder was performed, and the results are shown in fig. 2 and 3; observing the micro-morphology of the crushed ultrafine powder by using a scanning electron microscope, wherein the result is shown in figure 4; the solid phase synthesis powder after spray drying was analyzed for phase composition by X-ray diffractometry (XRD), respectively, and the results are shown in fig. 5; the spray-dried agglomerated powder was sampled and analyzed for morphology using a scanning electron microscope, and the results are shown in fig. 6.
As can be seen from FIG. 1, the original powder synthesized in example 1 had poor sphericity of particles, non-uniform particle size distribution, and poor flow properties.
From the EDS analysis in FIGS. 2 and 3, it can be seen that the original powder for solid phase synthesis contains elements such as strontium, cobalt, niobium, etc.
The microscopic morphology of the ultrafine powder can be seen from fig. 4, and the particle size is about 2 μm.
From fig. 5, it can be seen that the phase of the powder did not change significantly before and after spray-drying, demonstrating that the physical properties of the original powder did not change before and after spray-drying.
From fig. 6, it can be seen that the powder after spray drying has more uniform distribution and high sphericity than the ultra-fine powder.
In conclusion, the preparation method of the high-performance perovskite oxide powder for thermal spraying provided by the invention is simple and efficient, has no pollution, can improve the stable compounding probability of the powder and the yield of the powder, and can granulate and agglomerate the superfine powder into micron powder suitable for thermal spraying again under the condition of not changing the performance of the powder. The prepared agglomerated powder for thermal spraying has high fluidity, uniform powder particle size distribution, high sphericity and stable performance.
The high-performance perovskite oxide powder for thermal spraying provided by the invention has the advantages of higher fluidity, more uniform powder particle size distribution, high sphericity and stable performance, and is very suitable for being applied to thermal spraying.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of high-performance perovskite type oxide powder for thermal spraying is characterized by comprising the following steps:
re-granulating the perovskite type oxide superfine powder with the powder particle size of 1-3 mu m, wherein the re-granulation comprises the following steps:
performing primary ball milling mixing on the superfine powder, the solvent and the first dispersing agent to obtain first slurry, and performing secondary ball milling mixing on the first slurry and the binder to obtain second slurry;
the second slurry is spray granulated and then calcined.
2. The method for producing a high-performance perovskite-type oxide powder for thermal spraying according to claim 1,
the solvent comprises at least one of water and ethanol;
preferably, the water is deionized water;
more preferably, the mass ratio of the solvent to the ultrafine powder is 1.22-2.33: 1.
3. The preparation method of the high-performance perovskite oxide powder for thermal spraying according to claim 1, wherein the mass ratio of the ball milling medium to the ultrafine powder for each ball milling is 1-3: 1;
preferably, the ball milling medium comprises zirconia balls with the particle sizes of 4-8 mm, 8-12 mm and 18-22 mm respectively; more preferably, the number ratio of zirconia balls of three particle sizes is 8:4: 1;
preferably, the rotating speed of each ball milling is 200-400 rpm;
preferably, the time of each ball milling is 2-4 h.
4. The method for producing a high-performance perovskite oxide powder for thermal spraying according to claim 1, wherein the mass ratio of the first dispersant, the binder and the ultrafine powder is 3 to 10:3 to 12: 100;
preferably, the first dispersant is polyacrylic acid;
preferably, the binder is polyvinylpyrrolidone.
5. The method for preparing a high-performance perovskite oxide powder for thermal spraying according to any one of claims 1 to 4, wherein the process conditions for spray granulation are as follows: the feeding speed is 50-100 ml/min, the inlet temperature is 230-300 ℃, the outlet temperature is 60-130 ℃, the pressure in the cavity is 1-2 bar, and the atomizer is adjusted to be 3-6 m3/h。
6. The method for producing a high-performance perovskite oxide powder for thermal spraying according to any one of claims 1 to 4, characterized in that the calcination temperature is 300 to 500 ℃;
preferably, the calcination heat preservation time is 4-8 h.
7. The method for producing a high-performance perovskite oxide powder for thermal spraying according to any one of claims 1 to 4, characterized in that the perovskite oxide has a general structural formula:
SrCo1-xNbxO3-δwherein x is more than or equal to 0.1 and less than or equal to 0.25, delta is an oxygen vacancy, and delta is more than or equal to 0.475 and less than or equal to 0.55;
preferably, the synthesis method of the perovskite type oxide is as follows: the preparation method comprises the following steps of proportioning according to the structural general formula: SrCO3、Co3O4And Nb2O5Mixing and ball-milling, and synthesizing original powder by a solid-phase reaction;
drying the original powder obtained by ball milling, and roasting at 1000-1200 ℃;
preferably, the perovskite type oxide is synthesized and added with the preparation raw materials during ball milling, and the perovskite type oxide also comprises a second dispersing agent; more preferably, the second dispersant comprises at least one of ethanol and ethylene glycol; further preferably, the ratio of the addition amount of the second dispersing agent to the total mass of the preparation raw materials is 1.22-2.33: 1;
preferably, the mass ratio of a ball milling medium to a preparation raw material is 1-3: 1 when the perovskite type oxide is synthesized and ball milling is carried out; more preferably, the perovskite type oxide is synthesized, and a ball milling medium is a stainless steel ball with the particle size of 4-8 μm during ball milling;
preferably, the ball milling time for ball milling is 12-24 h when the perovskite type oxide is synthesized;
preferably, the drying is carried out under the vacuum condition of 80-100 ℃; further preferably, the drying time is 1-2 h;
preferably, the roasting time is 12-20 h.
8. The method for producing a high-performance perovskite-type oxide powder for thermal spraying according to any one of claims 1 to 4, further comprising, before re-granulating the ultrafine powder: carrying out superfine treatment on the original powder of the perovskite type oxide, wherein the superfine treatment comprises the following steps:
crushing the original powder in a jet mill, wherein the pressure of crushing airflow is 0.8-1.0 MPa, the feeding speed of the powder is 80-100 g/min, the height of a discharge port is 15-20mm, and the crushing times are 2-3 times;
preferably, the breaking gas stream is compressed air.
9. A high-performance perovskite oxide powder for thermal spraying, which is characterized by being prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the high performance perovskite oxide powder for thermal spraying according to claim 9 in thermal spraying.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911407856.XA CN111057985A (en) | 2019-12-31 | 2019-12-31 | High-performance perovskite type oxide powder for thermal spraying and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911407856.XA CN111057985A (en) | 2019-12-31 | 2019-12-31 | High-performance perovskite type oxide powder for thermal spraying and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111057985A true CN111057985A (en) | 2020-04-24 |
Family
ID=70305330
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911407856.XA Pending CN111057985A (en) | 2019-12-31 | 2019-12-31 | High-performance perovskite type oxide powder for thermal spraying and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111057985A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111634950A (en) * | 2020-06-28 | 2020-09-08 | 北京理工大学重庆创新中心 | Preparation method of perovskite type high-emissivity spherical agglomerated powder |
CN111807840A (en) * | 2020-07-17 | 2020-10-23 | 北京理工大学 | Preparation method of spherical high-emissivity powder for spraying |
CN112299827A (en) * | 2020-10-21 | 2021-02-02 | 先导薄膜材料(广东)有限公司 | Granulating method of ceramic oxide recovery powder |
CN113578464A (en) * | 2021-07-30 | 2021-11-02 | 深圳陶陶科技有限公司 | Method for improving sphericity of inorganic powder and spherical inorganic powder |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1081778A1 (en) * | 1998-04-21 | 2001-03-07 | Toto Ltd. | Solid electrolyte fuel cell and method of producing the same |
CN101254421A (en) * | 2007-12-10 | 2008-09-03 | 中国科学技术大学 | Two-phase composite compact ceramic oxygen permeable membrane and method of preparing the same |
CN103232246A (en) * | 2013-02-20 | 2013-08-07 | 国网智能电网研究院 | Preparation method of thermal spraying powder for ferrite corrosion-resistant coating |
CN106365636A (en) * | 2016-08-26 | 2017-02-01 | 中国科学院上海硅酸盐研究所 | High-Curie-temperature strontium-barium niobate pyroelectric ceramic material and preparation method thereof |
CN108530062A (en) * | 2018-05-14 | 2018-09-14 | 广东省新材料研究所 | A kind of superhigh temperature thermal barrier coating hollow structure powder and the preparation method and application thereof, superhigh temperature thermal barrier coating |
-
2019
- 2019-12-31 CN CN201911407856.XA patent/CN111057985A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1081778A1 (en) * | 1998-04-21 | 2001-03-07 | Toto Ltd. | Solid electrolyte fuel cell and method of producing the same |
CN101254421A (en) * | 2007-12-10 | 2008-09-03 | 中国科学技术大学 | Two-phase composite compact ceramic oxygen permeable membrane and method of preparing the same |
CN103232246A (en) * | 2013-02-20 | 2013-08-07 | 国网智能电网研究院 | Preparation method of thermal spraying powder for ferrite corrosion-resistant coating |
CN106365636A (en) * | 2016-08-26 | 2017-02-01 | 中国科学院上海硅酸盐研究所 | High-Curie-temperature strontium-barium niobate pyroelectric ceramic material and preparation method thereof |
CN108530062A (en) * | 2018-05-14 | 2018-09-14 | 广东省新材料研究所 | A kind of superhigh temperature thermal barrier coating hollow structure powder and the preparation method and application thereof, superhigh temperature thermal barrier coating |
Non-Patent Citations (1)
Title |
---|
张启龙: "《中国战略性新兴产业 新材料 功能陶瓷材料与器件》", 31 December 2017 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111634950A (en) * | 2020-06-28 | 2020-09-08 | 北京理工大学重庆创新中心 | Preparation method of perovskite type high-emissivity spherical agglomerated powder |
CN111634950B (en) * | 2020-06-28 | 2021-10-22 | 北京理工大学重庆创新中心 | Preparation method of perovskite type high-emissivity spherical agglomerated powder |
CN111807840A (en) * | 2020-07-17 | 2020-10-23 | 北京理工大学 | Preparation method of spherical high-emissivity powder for spraying |
CN111807840B (en) * | 2020-07-17 | 2021-10-08 | 北京理工大学 | Preparation method of spherical high-emissivity powder for spraying |
CN112299827A (en) * | 2020-10-21 | 2021-02-02 | 先导薄膜材料(广东)有限公司 | Granulating method of ceramic oxide recovery powder |
CN113578464A (en) * | 2021-07-30 | 2021-11-02 | 深圳陶陶科技有限公司 | Method for improving sphericity of inorganic powder and spherical inorganic powder |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111057985A (en) | High-performance perovskite type oxide powder for thermal spraying and preparation method and application thereof | |
US8546284B2 (en) | Process for the production of plasma sprayable yttria stabilized zirconia (YSZ) and plasma sprayable YSZ powder produced thereby | |
CN112358293B (en) | Powder for thermal barrier coating, preparation method and application thereof, and composite material with thermal barrier coating | |
KR102241096B1 (en) | Manufacturing method of garnet oxide type solid electrolyte having cubic structrue | |
CN110818430B (en) | Uniform high-entropy oxide ceramic submicron spherical powder and preparation method thereof | |
CN108033788B (en) | Preparation method of gadolinium zirconate-based ceramic material, gadolinium zirconate-based ceramic granulation powder for plasma spraying and preparation method thereof | |
WO2015015795A1 (en) | Siox powder manufacturing process and siox powder manufacturing apparatus | |
WO2014160445A1 (en) | Method for the use of slurries in spray pyrolysis for the production of non-hollow, porous particles | |
US9412486B2 (en) | Composite oxide powder for solid oxide fuel cell and its production method | |
CN112299827A (en) | Granulating method of ceramic oxide recovery powder | |
CN108417829A (en) | A kind of method that stabilization prepares the nickelic lithium battery tertiary material of monocrystalline | |
CN113564708B (en) | Method for preparing single crystal lithium nickel cobalt aluminum oxide | |
CN108017388B (en) | Lanthanum zirconate-based ceramic granulation powder for atmospheric plasma spraying and preparation method thereof | |
CN108530062B (en) | Hollow structure powder for ultrahigh-temperature thermal barrier coating, preparation method and application thereof, and ultrahigh-temperature thermal barrier coating | |
CN108640692A (en) | A kind of plasma physical vapor deposition rare earth oxide doping gadolinium zirconate powder and preparation method thereof | |
TWI829752B (en) | Powder for solid oxide fuel cell air electrode and manufacturing method thereof | |
CN113913723B (en) | Micron-sized porous-structure thermal barrier coating powder and preparation method thereof | |
CN108837968B (en) | Method for manufacturing spherical iron phosphate precursor with controllable particle size and pressure atomizing nozzle used in method | |
CN113683418B (en) | Tantalate spherical powder CaMoTa for thermal spraying 2 O 9 And a method for preparing the same | |
US20220045356A1 (en) | Method for producing lithium titanium phosphate | |
WO2014021028A1 (en) | Method for producing fuel electrode material for solid oxide fuel cell | |
CN108623315A (en) | A kind of preparation process of titanium alloy smelting oxidation yttrium powder | |
KR20150067546A (en) | Metal iron granule and the manufacturing method of the same | |
WO2024032829A1 (en) | Anti-sintering high-entropy ceramic thermal barrier coating powder material for plasma spraying physical vapor deposition, and preparation method therefor | |
KR100491677B1 (en) | METHOD FOR PREPARING OF CeO2 NANO POWDER |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200424 |
|
RJ01 | Rejection of invention patent application after publication |