CN112608161A - Preparation method of metal toughening type rare earth silicate powder - Google Patents

Preparation method of metal toughening type rare earth silicate powder Download PDF

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CN112608161A
CN112608161A CN202110003257.2A CN202110003257A CN112608161A CN 112608161 A CN112608161 A CN 112608161A CN 202110003257 A CN202110003257 A CN 202110003257A CN 112608161 A CN112608161 A CN 112608161A
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rare earth
earth silicate
metal
powder
sio
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张乐
李其连
马国佳
王纯
靳磊
周海滨
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AVIC Beijing Aeronautical Manufacturing Technology Research Institute
AVIC Manufacturing Technology Institute
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Abstract

The invention discloses a preparation method of metal toughening type rare earth silicate powder, which comprises the following steps: mixing rare earth oxide powder and SiO2Putting four materials of powder, metal/alloy powder and a binder into a ball mill, and carrying out ball milling for a first set time; placing the mixed material on a press to be pressed under the condition of normal temperature to obtain a first pressed blank body; carrying out vacuum degreasing and calcining on the first pressed green body to obtain metal toughening type rare earth silicate clinker; and crushing and screening the metal toughening type rare earth silicate clinker to obtain metal toughening type rare earth silicate powder. The preparation method of the metal toughening type rare earth silicate powder aims at solving the problem that the rare earth silicate powder has higher toughness after being prepared into a coatingPoor high temperature oxidation resistance.

Description

Preparation method of metal toughening type rare earth silicate powder
Technical Field
The invention belongs to the technical field of powder preparation, and particularly relates to a preparation method of metal toughening type rare earth silicate powder.
Background
The surface temperature of the hot end part of the new generation of aeroengine with high thrust-weight ratio reaches more than 1400 ℃, which exceeds the temperature range which can be born by the traditional nickel-based high-temperature alloy. The silicon carbide continuous fiber toughened silicon carbide ceramic matrix composite (SiCf/SiC for short) has the characteristics of low density, high strength, high modulus, oxidation resistance, high fracture strength at high temperature and the like, and is expected to replace high-temperature alloy to be applied to hot end parts of aero-engines. However, when SiCf/SiC is applied to hot end parts of aero-engines, SiC can be oxidized to generate SiO in the high-temperature water-oxygen coupled gas environment of aero-engines2，SiO2Reacting with steam to form volatile Si (OH)4(as shown in formula 1), which causes rapid degradation of material properties, the most effective way to prepare an Environmental Barrier Coating (EBC) on the surface of the SiCf/SiC substrate is to prepare the EBC, which is a surface protective coating for improving the Environmental stability of the SiCf/SiC composite material component.
The data report at home and abroad and the earlier research of patent application units show that Yb2SiO5、Er2SiO5、Gd2SiO5，Yb2Si2O7The rare earth silicates have the physical and chemical properties of high melting point (generally over 1800 ℃), extremely low high-temperature oxygen permeability, low Young modulus, low thermal conductivity, low saturated vapor pressure, lower thermal expansion coefficient and the like, and have good ultrahigh-temperature chemical stability and CMAS (CaO-MgO-Al) resistance2O3-SiO2) The corrosion capability makes it an important material for the new generation of EBC surface layer.
The rare earth silicate ceramic has high melting point, high hardness, low thermal conductivity and good oxidation resistance, and is considered as a key research material of a future environmental barrier coating. However, in the rare earth silicate material, the bonding bonds between atoms are covalent bonds and ionic bonds, the covalent bonds have obvious directionality and saturation, and the repulsion is large when the same number of ions of the ionic bonds are close to each other, so that the rare earth silicate ceramic mainly composed of the ionic bonds and the covalent bonds has few slip systems and generally breaks before slip occurs, and the brittleness problem of the silicate material is one of the main problems restricting the use of the rare earth silicate ceramic. The toughening mechanism of the ceramic material mainly comprises: phase transformation toughening, microcrack toughening, crack deflection and bridging (adding a second phase, nitride, carbide or metal), whisker/fiber toughening, domain transfer and twin toughening, and self-toughening.
In recent years, the shortage of short plates of high-performance aircraft engines in China is increasingly obvious, the national demand for high-performance CFCC-SiC-based hot end parts is more urgent, and the EBC on the surface of the CFCC-SiC part is required to have better toughness besides the high-temperature resistance, so that higher requirements are also put forward on the toughness of the rare earth silicate powder.
It can be known from the closely related patents and literatures that the main method for preparing the rare earth silicate for the environmental barrier coating at present is as follows: solid phase reaction method, spray drying method, solid diffusion reaction and spray drying method, organic solvent-coprecipitation method, sol-gel method, liquid phase reaction method, molten salt method, hydrothermal method. The main method for toughening the coating is to add Yb2Si2O7(or Yb)2SiO5) Yb is added into the coating2Si2O7Whiskers, but this method does not allow the direct preparation of Yb2Si2O7Whisker toughened Yb2Si2O7(or Yb)2SiO5) Powder and production of Yb2Si2O7Whisker and Yb2Si2O7、Yb2SiO5The liquid phase method is adopted when the powder is prepared, and the defects of liquid pollution, more steps, low efficiency and the like exist.
In the process of the rare earth silicate service, except water-oxygen corrosion, the rare earth silicate is also subjected to high-temperature oxidation, and Yb added into the rare earth silicate2Si2O7The whisker is also rare earth silicate essentially, and the additive cannot obviously improve the high-temperature oxidation resistance of the powder.
In view of the above, those skilled in the art need to provide a method for preparing a metal toughened rare earth silicate powder to solve the problems of poor toughness and poor high temperature oxidation resistance after the rare earth silicate powder is prepared into a coating.
Disclosure of Invention
Technical problem to be solved
The invention aims to solve the technical problems that the rare earth silicate powder prepared into a coating has poor toughness and insufficient high-temperature oxidation resistance.
(II) technical scheme
The first aspect of the invention provides a preparation method of metal toughening type rare earth silicate powder, which comprises the following steps:
mixing rare earth oxide powder and SiO2Putting four materials of powder, metal/alloy powder and a binder into a ball mill, and carrying out ball milling for a first set time;
placing the mixed material on a press to be pressed under the condition of normal temperature to obtain a first pressed blank body;
carrying out vacuum degreasing and calcining on the first pressed green body to obtain metal toughening type rare earth silicate clinker;
and crushing and screening the metal toughening type rare earth silicate clinker to obtain metal toughening type rare earth silicate powder.
Further, the rare earth oxide powder is Yb2O3、Lu2O3、Er2O3、Gd2O3And Y2O3One of (1); the metal/alloy is mainly at least one of Pt, Rh, Ir, Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt and Ir-Al.
Further, the first set time is 6-12 h.
Further, the rare earth silicate powder is Yb2SiO5、Yb2Si2O7、Lu2SiO5、Lu2Si2O7、Er2SiO5、Gd2SiO5And Y2SiO5One kind of (1).
The second aspect of the invention provides a preparation method of metal toughening type rare earth silicate powder, which comprises the following steps:
mixing rare earth oxide powder and SiO2Putting the powder and the binder into a ball mill, and performing ball milling for a second set time;
placing the mixed material on a press to be pressed under the condition of normal temperature to obtain a second pressed blank body;
calcining the second pressed green body to obtain rare earth silicate clinker;
crushing and screening the rare earth silicate clinker to obtain rare earth silicate powder;
and preparing the metal toughening type rare earth silicate powder by using the rare earth silicate powder and the metal/alloy powder through a mixing method or a spray drying sintering method.
Further, the rare earth oxide powder is one of Yb2O3, Lu2O3, Er2O3, Gd2O3 and Y2O 3; the metal/alloy is mainly one or more of Pt, Rh, Ir, Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt and Ir-Al.
Further, calcining the second green compact to obtain rare earth silicate clinker, which specifically comprises:
the temperature rise rate is 8 ℃/min to 15 ℃/min during calcination, the calcination temperature is 1300 ℃ to 1700 ℃, and the calcination time is 1h to 2h, so that the rare earth silicate clinker is obtained.
Further, the mixing method is a dry mixing method of a mixer;
the dry mixing of the mixer is specifically as follows: and putting the rare earth silicate powder and the metal/alloy powder into a mixer, and mixing for 8-15 h.
Further, the mixing method is a ball mill wet mixing method;
the wet mixing method for the ball mill specifically comprises the following steps: putting the rare earth silicate powder and the metal/alloy powder into a ball mill;
adding alcohol, and mixing materials on a ball mill for 8-12 hours;
and (3) mixing the materials, taking out the metal toughening type rare earth silicate powder and drying.
Further, the spray drying sintering method specifically comprises the following steps:
putting the rare earth silicate powder, the metal/alloy powder and the binder into a ball mill, and mixing for 8-15 hours;
pouring the material slurry mixed by the ball mill into a spray dryer for spray drying granulation to obtain spray-dried powder;
putting the powder after spray drying into a vacuum sintering furnace, sintering and cooling the blank to obtain metal rare earth silicate clinker after vacuum sintering;
and crushing and screening the metal rare earth silicate clinker after vacuum sintering to obtain the metal toughening type rare earth silicate powder.
Further, the inlet temperature of the spray dryer is 300-360 ℃, the outlet temperature is 140-170 ℃, and the feeding speed is 30-50 mL/min.
(III) advantageous effects
The technical scheme of the invention has the following advantages:
the preparation method of the metal toughening type rare earth silicate powder provided by the invention comprises the following steps: mixing rare earth oxide powder and SiO2Putting four materials of powder, metal/alloy powder and a binder into a ball mill, and carrying out ball milling for a first set time; placing the mixed material on a press to be pressed under the condition of normal temperature to obtain a first pressed blank body; carrying out vacuum degreasing and calcining on the first pressed green body to obtain metal toughening type rare earth silicate clinker; and crushing and screening the metal toughening type rare earth silicate clinker to obtain metal toughening type rare earth silicate powder. The preparation method can directly synthesize the toughened rare earth silicate powder material, and has the advantages of large one-time furnace discharge amount, high efficiency and relatively small pollution. The metal toughening type rare earth silicate powder is obtained by adding dispersed metal (or alloy) into rare earth silicate, and has the toughness and bending resistance of metal materials, and the high temperature resistance and water-oxygen corrosion resistance of silicate materials. After the powder is prepared into a coating by thermal spraying, the coating has more excellent bonding strength and anti-stripping capability compared with the rare earth silicate without metal.The metal additives are mainly metals such as platinum (Pt), rhodium (Rh), iridium (Ir) and the like, the alloys are mainly alloys such as Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt, Ir-Al and the like, the oxidation resistance temperature of the metals or alloys is above 1300 ℃, and the high temperature oxidation resistance of the rare earth silicate can be obviously improved while toughening.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a metal-toughened rare earth silicate powder according to an embodiment of the present invention;
FIG. 2 is a temperature rise graph of degreasing and calcining in the preparation method of the metal toughened rare earth silicate powder according to the embodiment of the present invention;
fig. 3 is a schematic flow chart of another method for preparing metal-toughened rare earth silicate powder according to an embodiment of the present invention.
In the figure:
A. a room temperature stage; B. a degreasing stage; C. a calcination stage; D. and (5) a furnace cooling stage.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In describing the present invention, it is to be understood that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In order to improve the toughness of the EBC coating on the hot-end part of the aero-engine prepared from the CFCC-SiC material and improve the stress distribution of the coating, it is necessary to firstly prepare metal (or alloy) toughening type rare earth silicate powder. The prior patent and literature do not report the method for directly preparing metal (or alloy) toughened rare earth silicate powder, and the liquid phase method is mainly adopted for toughening the coating to respectively prepare Yb2Si2O7Whisker and Yb2SiO5Powder and Yb2Si2O7Preparing Yb from the powder by ultrasonic-double-pulse hydrothermal electrophoretic deposition (or electromagnetic induction heating-double-pulse electrophoretic deposition)2Si2O7Whisker toughened Yb2Si2O7(or Yb)2SiO5) The preparation method of the composite coating adopts a liquid phase method, and has the defects of liquid pollution, more steps, low efficiency and the like.
According to a first aspect of embodiments of the present invention, there is provided a method for preparing a metal-toughened rare earth silicate powder, as shown in fig. 1, including the steps of:
s101, mixing rare earth oxide powder and SiO2Putting four materials of powder, metal/alloy powder and a binder into a ball mill, and carrying out ball milling for a first set time;
s102, placing the mixed material on a press to be pressed under the normal temperature condition to obtain a first pressed blank body;
s103, carrying out vacuum degreasing and calcining on the first pressed blank to obtain metal toughening type rare earth silicate clinker;
and S104, crushing and screening the metal toughening type rare earth silicate clinker to obtain metal toughening type rare earth silicate powder.
In this embodiment, in step S101, the selected metal/alloy has high melting point and high temperature oxidation resistance, and the metal is mainly platinum (Pt), rhodium (Rh), iridium (Ir), and the like; the alloy mainly comprises Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt, Ir-Al and the like. The metal/alloy is mainly one or more of platinum (Pt), rhodium (Rh), iridium (Ir), Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt and Ir-Al.
In step S103, the room temperature is raised to 100 ℃, and the temperature raising speed is 8 ℃/min to 15 ℃/min; the temperature is 100-600 ℃ which is a degreasing temperature range, and the temperature rise speed is 1-3 ℃/min; the temperature rise rate is 8 ℃/min to 15 ℃/min at the temperature of 600 ℃ to the calcination temperature (a certain temperature of 1300 ℃ to 1700 ℃), and after reaching the calcination temperature, the temperature is preserved and the calcination is carried out for 1h to 2h, so as to obtain the calcined metal toughening type silicate clinker. The vacuum degree of vacuum calcination is 0.1 × 10-3～1.0×10-3Pa is between Pa.
The metal/alloy does not react during vacuum calcination, the rare earth oxide and SiO2The main reactions that occur are as follows:
Yb2O3+SiO2→Yb2SiO5；
Yb2O3+2SiO2→Yb2Si2O7；
Lu2O3+SiO2→Lu2SiO5；
Lu2O3+2SiO2→Lu2Si2O7；
Er2O3+SiO2→Er2SiO5；
Gd2O3+SiO2→Gd2SiO5；
Y2O3+SiO2→Y2SiO5；
note: from rare earth oxide and SiO in raw materials2The Yb is obtained by determining the molar ratio and the calcination temperature2SiO5Is also Yb2Si2O7。
In some alternative embodiments, the rare earth oxide powder is Yb2O3、Lu2O3、Er2O3、Gd2O3And Y2O3One kind of (1).
In some optional embodiments, the first set time is 6h to 12 h.
In some alternative embodiments, the rare earth silicate powder is Yb2SiO5、Yb2Si2O7、Lu2SiO5、Lu2Si2O7、Er2SiO5、Gd2SiO5And Y2SiO5One kind of (1).
In one embodiment, the method is used to prepare Pt toughened Yb2Si2O7The powder is exemplified:
(1) 40kg of Yb with a particle size of-53 to +15 μm was weighed2O3Powder, 13kg of SiO with a particle size of-53 to +15 μm2Powder, 1.5kg of particle size10 mu m to +2.6 mu m of mPT powder and 1kg of polyvinyl alcohol with the granularity of-74 mu m to +15 mu m are put into a ball mill and ball-milled for 8 hours.
(2) And (3) pressing the mixed material on a press under the condition of normal temperature, wherein the pressing pressure is 25t, and obtaining a blank with the pressing diameter of 60mm and the height of 20 mm.
(3) And (4) carrying out vacuum degreasing and calcining on the pressed green body. The heating curve of degreasing and calcining is shown in figure 2, the temperature of the room temperature stage A is not changed, the room temperature is heated to 100 ℃ after the degreasing stage B, and the heating speed is 10 ℃/min; the temperature of 100-600 ℃ is a degreasing temperature range, and the temperature rise speed is 2 ℃/min; entering a calcination stage C at the temperature of 600-1500 ℃, the heating rate of 10 ℃/min, keeping the temperature and calcining for 1.5h after the temperature reaches 1500 ℃ to obtain the calcined metal toughened silicate clinker, wherein the vacuum degree of the vacuum calcination is 0.1 multiplied by 10-3～1.0×10-3Pa and finally in the furnace cooling stage D, the temperature will drop rapidly from 1500 ℃.
Yb in vacuum calcination2O3And SiO2The reactions that occur are shown below:
Yb2O3+2SiO2→Yb2Si2O7。
(4) the calcined Pt metal is toughened into Yb by a crusher2Si2O7Crushing the clinker, and sieving by a vibrating screen to obtain the Pt toughened Yb with the granularity of-106 to +45 mu m2Si2O7And (3) powder.
According to a second aspect of the embodiments of the present invention, there is provided a method for preparing a metal-toughened rare earth silicate powder, as shown in fig. 3, including the following steps:
s201, mixing rare earth oxide powder and SiO2Putting the powder and the binder into a ball mill, and performing ball milling for a second set time;
s202, placing the mixed material on a press to be pressed under the normal temperature condition to obtain a second pressed blank body;
s203, calcining the second pressed green body to obtain rare earth silicate clinker;
s204, crushing and screening the rare earth silicate clinker to obtain rare earth silicate powder;
s205, preparing the metal toughening type rare earth silicate powder by mixing the rare earth silicate powder and the metal/alloy powder through a mixing method or a spray drying sintering method.
In this embodiment, in step S201, the second set time is 6h to 12 h.
In step S203, the room temperature is increased to 100 ℃, and the temperature increasing speed is 8 ℃/min to 15 ℃/min; the temperature is 100-600 ℃ which is a degreasing temperature range, and the temperature rise speed is 1-3 ℃/min; the temperature rise rate is 8 ℃/min to 15 ℃/min at the temperature of 600 ℃ to the calcination temperature (a certain temperature of 1300 ℃ to 1700 ℃), and after reaching the calcination temperature, the temperature is preserved and the calcination is carried out for 1h to 2h, so as to obtain the calcined metal toughening type silicate clinker. The vacuum degree of vacuum calcination is 0.1 × 10-3～1.0×10-3Pa is between Pa.
The metal/alloy does not react during vacuum calcination, the rare earth oxide and SiO2The main reactions that occur are as follows:
Yb2O3+SiO2→Yb2SiO5；
Yb2O3+2SiO2→Yb2Si2O7；
Lu2O3+SiO2→Lu2SiO5；
Lu2O3+2SiO2→Lu2Si2O7；
Er2O3+SiO2→Er2SiO5；
Gd2O3+SiO2→Gd2SiO5；
Y2O3+SiO2→Y2SiO5；
note: from rare earth oxide and SiO in raw materials2The Yb is obtained by determining the molar ratio and the calcination temperature2SiO5Is also Yb2Si2O7。
In step S205, after the rare earth silicate powder is prepared, two methods are mainly used for preparing the metal toughened rare earth silicate powder: the first method is that rare earth silicate and metal/alloy are directly mixed to obtain rare earth toughening type rare earth silicate powder; the second method is to prepare the metal toughening rare earth silicate powder by adopting a spray drying and sintering method. The metal/alloy is mainly one or more of platinum (Pt), rhodium (Rh), iridium (Ir), Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt and Ir-Al.
In some alternative embodiments, the second green compact is calcined to obtain a rare earth silicate clinker, specifically:
the temperature rise rate is 8 ℃/min to 15 ℃/min during calcination, the calcination temperature is 1300 ℃ to 1700 ℃, and the calcination time is 1h to 2h, so that the rare earth silicate clinker is obtained.
In some alternative embodiments, the rare earth oxide powder is Yb2O3、Lu2O3、Er2O3、Gd2O3And Y2O3One of (1); the metal/alloy is mainly one or more of platinum (Pt), rhodium (Rh), iridium (Ir), Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt and Ir-Al.
In some alternative embodiments, the mixing process is a compounder dry mixing process;
the dry mixing of the mixer specifically comprises the following steps: and (3) putting the rare earth silicate powder and the metal/alloy powder into a mixer, and mixing for 8-15 hours.
In some alternative embodiments, the mixing process is a ball mill wet mixing process;
the wet mixing method for the ball mill specifically comprises the following steps: putting rare earth silicate powder and metal/alloy powder into a mixer;
adding alcohol, and mixing materials on a ball mill for 8-12 hours;
and (3) mixing the materials, taking out the metal toughening type rare earth silicate powder and drying.
In some alternative embodiments, the spray-dry sintering process specifically comprises the steps of:
putting the rare earth silicate powder, the metal/alloy powder and the binder into a ball mill, and mixing for 8-15 hours;
pouring the material slurry mixed by the ball mill into a spray dryer for spray drying granulation to obtain spray-dried powder;
putting the powder after spray drying into a vacuum sintering furnace, sintering and cooling the blank to obtain metal rare earth silicate clinker after vacuum sintering;
and crushing and screening the metal rare earth silicate clinker after vacuum sintering to obtain the metal toughening type rare earth silicate powder.
In some alternative embodiments, the spray dryer has an inlet temperature of 300 ℃ to 360 ℃, an outlet temperature of 140 ℃ to 170 ℃, and a feed rate of 30mL/min to 50 mL/min.
In a specific embodiment, Ir-Al alloy toughened Gd is prepared2SiO5The powder is exemplified:
1、Gd2SiO5preparation of powder
(1) Weighing 36kg of Gd with the granularity of-45 mu m to +20 mu m2O3Powder, 6kg of SiO with a particle size of-53 to +15 μm2Powder and 1.2kg of polyvinyl alcohol with the granularity of-74 mu m to +15 mu m are put into a ball mill and are ball-milled for 6 hours.
(2) And (3) pressing the mixed material on a press at the normal temperature with the pressing pressure of 30t to obtain a blank with the pressing diameter of 60mm and the height of 20 mm.
(3) And degreasing and calcining the pressed green body in the atmosphere. Heating the mixture to 100 ℃ at the room temperature, wherein the heating speed is 10 ℃/min; the temperature of 100-600 ℃ is a degreasing temperature range, and the temperature rise speed is 2 ℃/min; heating rate of 600-1580 ℃ (calcination temperature) is 10 ℃/min, and after reaching 1580 ℃, heat preservation and calcination are carried out for 1h to obtain calcined Gd2SiO5And (3) clinker.
The reactions that occur during calcination are as follows:
Gd2O3+SiO2→Gd2SiO5。
(4) crushing the calcined Gd with a crusher2SiO5Crushing and screening the clinker to obtain Gd with the granularity of-90 to +11 mu m2SiO5And (3) powder.
2. Preparation of Pt-Rh (10 wt% Rh) alloy toughening type Gd by vacuum sintering2SiO5Powder of
(1) Weighing 10kg Gd with the granularity of-90 mu m to +11 mu m2SiO5The powder, 0.4kg of Pt-Rh (10 wt% Rh) alloy powder with the particle size of-53 mu m to +15 mu m, and a binder (150mL of n-octanol, 150mL of ethylene glycol, 900mL of PVP, 9000mL of water and the like) are put into a ball mill and mixed for 10 hours. Wherein the PVP is polyvinylpyrrolidone (polyvinylpyrrolidone).
(2) And pouring the material slurry mixed by the ball mill into a spray dryer for spray drying granulation (the inlet temperature is set to be 360 ℃, the outlet temperature is set to be 160 ℃, and the feeding speed is 50mL/min), so as to obtain the powder after spray drying.
(3) And putting the powder after spray drying into a vacuum sintering furnace, and sintering and cooling the blank. Heating the spray dried powder from room temperature to sintering temperature (900 deg.C) at a heating rate of 10 deg.C/min for 1h, wherein the vacuum degree during sintering is 0.1 × 10-3～1.0×10-3Pa, furnace cooling to obtain Pt-Rh (10 wt% Rh) alloy toughened Gd2SiO5And (3) clinker.
(4) Toughening Gd of the intermetallic compound after vacuum sintering by a crusher2SiO5Crushing and screening the clinker to obtain gold Pt-Rh (10 wt% Rh) alloy toughened Gd with the granularity of-106 to +45 mu m2SiO5And (3) powder.
The embodiment of the invention provides a preparation method of metal toughening type rare earth silicate powder, a preparation process of the existing rare earth silicate powder, and Yb2Si2O7Compared with the whisker toughening type rare earth silicate, the whisker toughening type rare earth silicate has the following advantages:
1. the preparation method of the metal toughening type rare earth silicate powder adopts a new toughening mode and components to toughen rare earth silicate for environmental obstacles, obtains the metal toughening type rare earth silicate powder by adding dispersed metal/alloy into the rare earth silicate, has the toughness and bending resistance of metal materials and the high temperature resistance and the water and oxygen corrosion resistance of silicate materials, and has more excellent bonding strength and anti-stripping capability compared with the rare earth silicate without metal after the powder is prepared into a coating by thermal spraying;
2. the metal additives adopted by the preparation method of the metal toughening type rare earth silicate powder provided by the embodiment of the invention are mainly platinum (Pt), rhodium (Rh), iridium (Ir) and other metals, the alloys are mainly Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt, Ir-Al and other alloys, the oxidation resistance temperature of the metals or alloys is above 1300 ℃, and the high temperature oxidation resistance of the rare earth silicate can be obviously improved while toughening;
3. the preparation method of the metal toughening type rare earth silicate powder of the embodiment of the invention can mix rare earth oxide and SiO2Metal/alloy and binder, then preparing the metal toughening type rare earth silicate powder material by a one-time calcination method, and respectively preparing Yb compared with a liquid phase method2Si2O7Whisker and Yb2SiO5Preparing Yb from powder material by electromagnetic induction heating-double pulse electrophoretic deposition2Si2O7Whisker toughened Yb2SiO5The embodiment of the invention can directly synthesize the toughened rare earth silicate powder material of the composite coating, and has the advantages of large one-time furnace discharge amount, high efficiency and relatively small pollution.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the metal toughening type rare earth silicate powder is characterized by comprising the following steps:
mixing rare earth oxide powder and SiO2Putting four materials of powder, metal/alloy powder and a binder into a ball mill, and carrying out ball milling for a first set time;
placing the mixed material on a press to be pressed under the condition of normal temperature to obtain a first pressed blank body;
carrying out vacuum degreasing and calcining on the first pressed green body to obtain metal toughening type rare earth silicate clinker;
and crushing and screening the metal toughening type rare earth silicate clinker to obtain metal toughening type rare earth silicate powder.
2. The method for preparing metal-toughened rare earth silicate powder according to claim 1, wherein the rare earth oxide powder is Yb2O3、Lu2O3、Er2O3、Gd2O3And Y2O3One of (1); the metal/alloy is mainly one or more of Pt, Rh, Ir, Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt and Ir-Al.
3. The method for preparing metal toughened rare earth silicate powder according to claim 1, wherein the first set time is 6 to 12 hours.
4. The method for producing a metal-toughened rare earth silicate powder as claimed in claim 2, wherein the rare earth silicate powder is Yb2SiO5、Yb2Si2O7、Er2SiO5、Lu2SiO5、Lu2Si2O7、Gd2SiO5And Y2SiO5One kind of (1).
5. The preparation method of the metal toughening type rare earth silicate powder is characterized by comprising the following steps:
mixing rare earth oxide powder and SiO2Putting the powder and the binder into a ball mill, and performing ball milling for a second set time;
placing the mixed material on a press to be pressed under the condition of normal temperature to obtain a second pressed blank body;
calcining the second pressed green body to obtain rare earth silicate clinker;
crushing and screening the rare earth silicate clinker to obtain rare earth silicate powder;
and preparing the metal toughening type rare earth silicate powder by using the rare earth silicate powder and the metal/alloy powder through a mixing method or a spray drying sintering method.
6. The method for preparing metal-toughened rare earth silicate powder according to claim 5, wherein the rare earth oxide powder is one of Yb2O3, Lu2O3, Er2O3, Gd2O3 and Y2O 3; the metal/alloy is mainly one or more of Pt, Rh, Ir, Pt-Rh, Ir-Hf, Ir-Ta-Al, Ir-Pt and Ir-Al.
7. The method for preparing the metal toughening rare earth silicate powder according to claim 5, wherein the second green compact is calcined to obtain a rare earth silicate clinker, and the method specifically comprises the following steps:
the temperature rise rate is 8 ℃/min to 15 ℃/min during calcination, the calcination temperature is 1300 ℃ to 1700 ℃, and the calcination time is 1h to 2h, so that the rare earth silicate clinker is obtained.
8. The method for preparing the metal toughening rare earth silicate powder according to claim 5, wherein the mixing method is a dry mixing method by a mixer;
the dry mixing of the mixer is specifically as follows: and putting the rare earth silicate powder and the metal/alloy powder into a mixer, and mixing for 8-15 h.
9. The method for preparing metal toughened rare earth silicate powder according to claim 5, wherein the mixing method is a ball mill wet mixing method;
the wet mixing method for the ball mill specifically comprises the following steps:
putting the rare earth silicate powder and the metal/alloy powder into a mixer;
adding alcohol, and mixing materials on a ball mill for 8-12 hours;
and (3) mixing the materials, taking out the metal toughening type rare earth silicate powder and drying.
10. The method for preparing the metal toughened rare earth silicate powder according to claim 5, wherein the spray drying sintering method specifically comprises the following steps:
putting the rare earth silicate powder, the metal/alloy powder and the binder into a ball mill, and mixing for 8-15 hours;
pouring the material slurry mixed by the ball mill into a spray dryer for spray drying granulation to obtain spray-dried powder;
putting the powder after spray drying into a vacuum sintering furnace, sintering and cooling the blank to obtain metal rare earth silicate clinker after vacuum sintering;
and crushing and screening the metal rare earth silicate clinker after vacuum sintering to obtain the metal toughening type rare earth silicate powder.
CN202110003257.2A 2021-01-04 2021-01-04 Preparation method of metal toughening type rare earth silicate powder Pending CN112608161A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113999021A (en) * 2021-10-21 2022-02-01 辽宁科技大学 Method for modifying impurities of magnesium-based refractory material with controllable morphology

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101269960A (en) * 2008-04-30 2008-09-24 哈尔滨工业大学 Composite rare earth zirconate thermal barrier coating ceramic material and preparation method thereof
CN102560321A (en) * 2012-01-19 2012-07-11 中国科学院金属研究所 Yttrium silicate hot-spray composite powder and preparation method thereof
CN102732883A (en) * 2012-06-18 2012-10-17 北京科技大学 Precious metal particle dispersed toughened composite thermal barrier coating and its preparation method
US20160122877A1 (en) * 2013-09-13 2016-05-05 Institute Of Metal Research, Chinese Academy Of Sciences Surface Alloy Coating Composite material Used for High Temperature Resistant Material, Coating and Preparation Method Thereof
CN109837496A (en) * 2017-11-27 2019-06-04 深圳航发复合材料有限公司 A kind of preparation method of ytterbium silicate plasma spraying powder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101269960A (en) * 2008-04-30 2008-09-24 哈尔滨工业大学 Composite rare earth zirconate thermal barrier coating ceramic material and preparation method thereof
CN102560321A (en) * 2012-01-19 2012-07-11 中国科学院金属研究所 Yttrium silicate hot-spray composite powder and preparation method thereof
CN102732883A (en) * 2012-06-18 2012-10-17 北京科技大学 Precious metal particle dispersed toughened composite thermal barrier coating and its preparation method
US20160122877A1 (en) * 2013-09-13 2016-05-05 Institute Of Metal Research, Chinese Academy Of Sciences Surface Alloy Coating Composite material Used for High Temperature Resistant Material, Coating and Preparation Method Thereof
CN109837496A (en) * 2017-11-27 2019-06-04 深圳航发复合材料有限公司 A kind of preparation method of ytterbium silicate plasma spraying powder

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113999021A (en) * 2021-10-21 2022-02-01 辽宁科技大学 Method for modifying impurities of magnesium-based refractory material with controllable morphology

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Application publication date: 20210406