阅读说明：本技术 一种太阳能热发电用复合陶瓷管道材料的制备方法 (Preparation method of composite ceramic pipeline material for solar thermal power generation ) 是由 郑龙 于 2020-04-17 设计创作，主要内容包括：本发明涉及一种太阳能热发电用复合陶瓷管道材料的制备方法,属于陶瓷材料技术领域。本发明以三氧化二铁、氧化锌和氧化铜为原料,掺杂氧化铝和氧化镧通过球磨、压制处理制备出复合铁氧体作为靶材,以Al<Sub>2</Sub>O<Sub>3</Sub>陶瓷管作为基体,采用溅射成膜在基体表面溅射一层复合膜,制备出一种太阳能热发电用复合陶瓷管道材料；Al<Sub>2</Sub>O<Sub>3</Sub>和La<Sub>2</Sub>O<Sub>3</Sub>复合掺杂可以极大的提升铁氧体的耐热冲击性能,在该组掺杂下晶粒大小均匀,晶界清晰平直,气孔率非常低,这对提高耐热冲击性能非常有利；Al<Sub>2</Sub>O<Sub>3</Sub>和La<Sub>2</Sub>O<Sub>3</Sub>能够使晶粒均匀细化,晶界数量增多,使晶粒之间的结合更加紧密,增大了复合膜的致密性,使得制备的太阳能热发电用复合陶瓷管道材料具有良好的耐热冲击性能。(The invention relates to a preparation method of a composite ceramic pipeline material for solar thermal power generation, belonging to the technical field of ceramic materials. The invention takes ferric oxide, zinc oxide and copper oxide as raw materials, aluminum oxide and lanthanum oxide are doped, composite ferrite is prepared by ball milling and pressing treatment and is taken as a target material, and Al is taken as 2 O 3 The ceramic tube is used as a matrix, and a composite film is sputtered on the surface of the matrix by adopting sputtering film formation to prepare the composite ceramic pipeline material for solar thermal power generation; al (Al) 2 O 3 And La 2 O 3 The composite doping can be greatly improvedThe ferrite has the thermal shock resistance, and the doped ferrite has uniform crystal grain size, clear and straight crystal boundary and very low porosity, which is very favorable for improving the thermal shock resistance; al (Al) 2 O 3 And La 2 O 3 The method has the advantages that the crystal grains can be uniformly refined, the number of the crystal boundaries is increased, the combination among the crystal grains is tighter, the compactness of the composite membrane is increased, and the prepared composite ceramic pipeline material for solar thermal power generation has good thermal shock resistance.)

1. A preparation method of a composite ceramic pipeline material for solar thermal power generation is characterized by comprising the following specific preparation steps:

(1) mixing ferric oxide, zinc oxide and copper oxide according to the mass ratio of 9: 2 to obtain mixed powder, mixing the mixed powder with deionized water, carrying out ball milling treatment to obtain a mixture A, drying and sieving the mixture A to obtain an abrasive A, placing the abrasive A in a muffle furnace for roasting treatment, and cooling to room temperature to obtain a roasted product A;

(2) mixing the roasted material A, aluminum oxide, lanthanum oxide and deionized water according to the mass ratio of 10: 1: 2: 15, ball-milling for 5-6 h at the rotating speed of 400-500 r/min to obtain a mixture B, drying the mixture B in an oven at the temperature of 60-80 ℃ to constant weight, cooling to room temperature, sieving with an 80-100-mesh sieve to obtain an abrasive material B, placing the abrasive material B in a muffle furnace for heat preservation and sintering treatment, and cooling along with the furnace temperature to obtain a roasted material B;

(3) placing the roasted product B in a mould for pressing treatment to obtain a target material;

(4) mixing Al₂O₃Carrying out ultrasonic cleaning on the ceramic tube, naturally airing to obtain a matrix, and carrying out pre-sputtering treatment on the matrix to obtain a pre-sputtered matrix;

(5) and carrying out sputtering film forming treatment on the pre-sputtered substrate to obtain a semi-finished product, annealing and insulating the semi-finished product, and cooling to room temperature to obtain the composite ceramic pipeline material for solar thermal power generation.

2. The method for preparing a composite ceramic pipeline material for solar thermal power generation according to claim 1, characterized in that: the ball milling treatment step in the step (1) is as follows: mixing the mixed powder with deionized water according to the mass ratio of 1: 2, and ball-milling for 3-4 h at the rotating speed of 300-400 r/min.

3. The method for preparing a composite ceramic pipeline material for solar thermal power generation according to claim 1, characterized in that: the drying and screening treatment steps in the step (1) are as follows: and (3) drying the mixture A in an oven at the temperature of 60-80 ℃ to constant weight, cooling to room temperature, and sieving with a sieve of 80-100 meshes.

4. The method for preparing a composite ceramic pipeline material for solar thermal power generation according to claim 1, characterized in that: the roasting treatment step in the step (1) is as follows: and (3) placing the grinding material A in a muffle furnace, and roasting for 1-2 h at the temperature of 1000-1050 ℃.

5. The method for preparing a composite ceramic pipeline material for solar thermal power generation according to claim 1, characterized in that: the heat-preservation sintering treatment step in the step (2) is as follows: and (3) placing the grinding material B in a muffle furnace, and sintering for 2-3 h at the temperature of 1100-1150 ℃ in a heat preservation manner.

6. The method for preparing a composite ceramic pipeline material for solar thermal power generation according to claim 1, characterized in that: the pressing treatment step in the step (3) is as follows: and placing the roasted material B into a die with the diameter of 60mm and the thickness of 10mm, and pressing for 1-2 min under the pressure of 3-5 MPa.

7. The method for preparing a composite ceramic pipeline material for solar thermal power generation according to claim 1, characterized in that: the ultrasonic cleaning step in the step (4) is as follows: mixing Al₂O₃And ultrasonically cleaning the ceramic tube for 10-15 min by using acetone, absolute ethyl alcohol and deionized water respectively.

8. The method for preparing the composite ceramic pipeline material for solar thermal power generation according to claim 1, wherein the pre-sputtering treatment step in the step (4) is to pre-sputter the substrate with a vacuum degree of 3.0 × 10^-4Pa, the sputtering gas is high-purity argon, and the pre-sputtering is carried out for 20-30 min.

9. The method for preparing a composite ceramic pipeline material for solar thermal power generation according to claim 1, characterized in that: the sputtering film-forming process of step (5) comprises: and carrying out sputtering film forming treatment on the pre-sputtering substrate, wherein the sputtering power is 75-80W, and the sputtering pressure is 1.2-1.5 Pa.

10. The method for preparing a composite ceramic pipeline material for solar thermal power generation according to claim 1, characterized in that: the annealing and heat preservation step in the step (5) is as follows: annealing and insulating the semi-finished product for 1-2 h at the temperature of 300-350 ℃.

Technical Field

The invention relates to a preparation method of a composite ceramic pipeline material for solar thermal power generation, belonging to the technical field of ceramic materials.

Background

The heat transmission subsystem in the tower type solar thermal power generation device plays a role in heat energy transmission, and the transmission efficiency directly influences the solar thermal utilization efficiency, so that the requirements on heat transmission pipeline materials are strict and the basic requirements are as follows: (1) the heat loss of the heat transmission pipeline is small, namely the density of the material of the heat transmission pipeline is high, and the heat conductivity is as small as possible; (2) the high-temperature mechanical property and the thermal shock resistance are good, and material damage caused by cyclic thermal shock due to day and night temperature difference can be avoided; (3) good high-temperature performance, no deformation, high strength and the like under continuous high temperature; (4) the cost of heat transfer is low. At present, heat transmission pipeline materials for solar thermal power generation mainly use alloy pipelines, and the heat transmission efficiency is hindered by the defects of low use temperature, non-corrosion resistance and the like, so that a novel high-temperature pipeline material which can resist the temperature of more than 1000 ℃ and has good corrosion resistance and thermal stability is found, and the heat transmission pipeline material has very important significance for enriching the use range of the pipeline material from the aspects of theory and engineering application.

The solar thermal power generation pipeline material is similar to a thermal power generation pipeline material at present and is made of heat-resistant alloy steel, and the heat-resistant alloy steel has good heat resistance, oxidation resistance, high mechanical strength and the like at high temperature. The common heat-resistant steel for the power station pipeline parts is basically ferrite heat-resistant steel and austenite heat-resistant steel, and the ceramic pipeline material is expected to be a preferred material for the solar thermal power generation heat transmission pipeline due to the advantages of high temperature resistance, corrosion resistance and high temperature performance.

The ceramic has excellent performances of high temperature resistance, corrosion resistance, high strength and the like, and can be used as a high-temperature ceramic heat transmission pipeline material for solar thermal power generation. For commercialized Al₂O₃Ceramic tube, SiC ceramic tube, Si₃N₄The ceramic tube and the mullite ceramic tube and the cordierite ceramic tube with excellent performance can be potential materials of a solar thermal power generation heat transmission pipeline.

The SiC ceramic pipeline is mainly used for heating bodies in a metallurgical sintering furnace and a medium-frequency heating forging furnace. Because of the strong covalent bond property, the SiC ceramic pipeline has the advantages of high temperature resistance, corrosion resistance, good high-temperature stability, good thermal shock resistance and the like, and can still maintain excellent performance under the harsh conditions. However, the SiC ceramic tube has high preparation temperature, large porosity, poor sealing performance when used at high temperature, and high thermal conductivity, which can cause fast convection and heat transfer of the tube wall and affect the heat transfer efficiency of the heat transfer pipeline. Al (Al)₂O₃The ceramic tube has excellent qualities of high temperature resistance, wear resistance, corrosion resistance, excellent mechanical property, high hardness, stable chemical property and the like, but has high thermal expansion coefficient and thermal shock resistanceThe properties are poor.

The heat transmission pipeline for solar thermal power generation needs to have good air tightness, otherwise, the heat transmission medium can be leaked, and the heat transmission efficiency and the solar thermal power generation efficiency are affected. Aiming at the heat transfer medium of the third generation (high temperature air is more than 1000 ℃), stricter requirements are put forward on the air tightness of the heat transmission pipeline, namely the ceramic pipeline has high density and the water absorption rate is less than 0.5%. The sintering driving force of the sintered ceramic with high compactness and high strength is the surface energy of powder particles. According to the action mechanism of surface tension, the ceramic powder with smaller granularity, larger specific surface area and higher surface activity is adopted to prepare the ceramic, so that the sintering temperature of the ceramic can be obviously reduced, and the compactness of the ceramic is promoted.

The special sintering modes such as hot-pressing sintering, hot isostatic pressing sintering, microwave heating sintering, spark plasma sintering and the like can play a role in reducing the sintering temperature.

The hot-pressing sintering is to heat and pressurize the blank to compact the sample in a short time. Aiming at high-temperature ceramic materials (such as Al) difficult to sinter₂O₃、Si₃N₄、B₄C、SiC、TiB₂、ZrB₂Etc.) is an effective densification technique. Common Al₂O₃The complex phase ceramic tool bit is sintered by hot pressing, and the ceramic matrix composite material usually uses dispersed particles and the like as a second phase, and the hot pressing sintering is beneficial to the densification of the composite system and reduces the sintering temperature.

The hot isostatic pressing sintering and the hot pressing sintering are similar in principle, but the ceramic is subjected to the mutual action of balanced pressure in all directions, high temperature and high pressure in the heating process to densify the ceramic, for the HIP process of most ceramic materials, the required sintering temperature is only 50-70% of the melting point of the material, and the oxide ceramic and the composite ceramic with high strength can be prepared.

The microwave heating sintering utilizes the action of a microwave point magnetic field and a medium to generate dielectric loss to heat and sinter the surface and the inside of the ceramic, so that the internal heat gradient of the ceramic is reduced, and the ceramic is uniformly heated.

The discharge plasma sintering directly applies strong pulse current to a sample, realizes sintering by utilizing thermal effect and various field effects, and is a novel rapid sintering technology which is developed rapidly in recent years.

The heat-resistant alloy as the main material of the heat transmission pipeline has the defects of corrosion resistance, large high-temperature creep, high heat conductivity (fast heat dissipation), poor high-temperature stability and the like, so that the solar heat transmission efficiency is low; the high-temperature structural ceramic can replace heat-resistant alloy to be used under high-temperature harsh conditions due to the characteristics of high strength, heat resistance, wear resistance, corrosion resistance, low thermal conductivity and the like, but the reliability of the ceramic material in the actual use process is still a very concerned problem for a material user, and the reliability of the ceramic material comprises the aspects of high-temperature creep damage, brittle fracture, delayed fracture damage (subcritical crack propagation) and the like of the ceramic, so that the ceramic heat transmission pipeline needs to have good high-temperature performance and thermal performance, such as excellent high-temperature creep resistance, thermal shock resistance, low thermal conductivity and the like.

Disclosure of Invention

The technical problems to be solved by the invention are as follows: aiming at the problems of high thermal expansion coefficient and poor thermal shock resistance of the existing ceramic pipeline material, the preparation method of the composite ceramic pipeline material for solar thermal power generation is provided.

In order to solve the technical problems, the invention adopts the technical scheme that:

(1) mixing ferric oxide, zinc oxide and copper oxide according to the mass ratio of 9: 2 to obtain mixed powder, mixing the mixed powder with deionized water, carrying out ball milling treatment to obtain a mixture A, drying and sieving the mixture A to obtain an abrasive A, placing the abrasive A in a muffle furnace for roasting treatment, and cooling to room temperature to obtain a roasted product A;

(2) mixing the roasted material A, aluminum oxide, lanthanum oxide and deionized water according to the mass ratio of 10: 1: 2: 15, ball-milling for 5-6 h at the rotating speed of 400-500 r/min to obtain a mixture B, drying the mixture B in an oven at the temperature of 60-80 ℃ to constant weight, cooling to room temperature, sieving with an 80-100-mesh sieve to obtain an abrasive material B, placing the abrasive material B in a muffle furnace for heat preservation and sintering treatment, and cooling along with the furnace temperature to obtain a roasted material B;

(3) placing the roasted product B in a mould for pressing treatment to obtain a target material;

(4) mixing Al₂O₃Carrying out ultrasonic cleaning on the ceramic tube, naturally airing to obtain a matrix, and carrying out pre-sputtering treatment on the matrix to obtain a pre-sputtered matrix;

(5) and carrying out sputtering film forming treatment on the pre-sputtered substrate to obtain a semi-finished product, annealing and insulating the semi-finished product, and cooling to room temperature to obtain the composite ceramic pipeline material for solar thermal power generation.

The ball milling treatment step in the step (1) is as follows: mixing the mixed powder with deionized water according to the mass ratio of 1: 2, and ball-milling for 3-4 h at the rotating speed of 300-400 r/min.

The drying and screening treatment steps in the step (1) are as follows: and (3) drying the mixture A in an oven at the temperature of 60-80 ℃ to constant weight, cooling to room temperature, and sieving with a sieve of 80-100 meshes.

The roasting treatment step in the step (1) is as follows: and (3) placing the grinding material A in a muffle furnace, and roasting for 1-2 h at the temperature of 1000-1050 ℃.

The heat-preservation sintering treatment step in the step (2) is as follows: and (3) placing the grinding material B in a muffle furnace, and sintering for 2-3 h at the temperature of 1100-1150 ℃ in a heat preservation manner.

The pressing treatment step in the step (3) is as follows: and placing the roasted material B into a die with the diameter of 60mm and the thickness of 10mm, and pressing for 1-2 min under the pressure of 3-5 MPa.

The ultrasonic cleaning step in the step (4) is as follows: mixing Al₂O₃And ultrasonically cleaning the ceramic tube for 10-15 min by using acetone, absolute ethyl alcohol and deionized water respectively.

The pre-sputtering treatment step in the step (4) is to carry out pre-sputtering treatment on the substrate with the vacuum degree of 3.0 × 10^{- 4}Pa, the sputtering gas is high-purity argon, and the pre-sputtering is carried out for 20-30 min.

The sputtering film-forming process of step (5) comprises: and carrying out sputtering film forming treatment on the pre-sputtering substrate, wherein the sputtering power is 75-80W, and the sputtering pressure is 1.2-1.5 Pa.

The annealing and heat preservation step in the step (5) is as follows: annealing and insulating the semi-finished product for 1-2 h at the temperature of 300-350 ℃.

Compared with other methods, the method has the beneficial technical effects that:

(1) the invention takes ferric oxide, zinc oxide and copper oxide as raw materials, aluminum oxide and lanthanum oxide are doped, composite ferrite is prepared by ball milling and pressing treatment and is taken as a target material, and Al is taken as₂O₃The ceramic tube is used as a matrix, and a composite film is sputtered on the surface of the matrix by adopting sputtering film formation to prepare the composite ceramic pipeline material for solar thermal power generation; al (Al)₂O₃Can effectively inhibit Fe²⁺Can reduce loss, properly inhibit the growth of crystal grains, prevent abnormal growth of the crystal grains and prevent La from being generated₂O₃Can modify the density, high-temperature performance and hot blood performance of the composite membrane, and Al₂O₃And La₂O₃The thermal shock resistance of the ferrite can be greatly improved by composite doping, and the crystal grain size is uniform under the group of doping, the crystal boundary is clear and straight, the porosity is very low, so that the thermal shock resistance is very favorably improved; al (Al)₂O₃And La₂O₃The method has the advantages that the crystal grains can be uniformly refined, the number of the crystal boundaries is increased, the combination among the crystal grains is tighter, the compactness of the composite membrane is increased, and the prepared composite ceramic pipeline material for solar thermal power generation has good thermal shock resistance;

(2) the method comprises the steps of sputtering a layer of composite film on the surface of a substrate by a radio frequency magnetron sputtering method, accelerating electrons to move to an anode under the action of an electric field, colliding with argon atoms in the moving process, ionizing the argon atoms to generate argon ions and electrons, moving the electrons to the anode under the action of the electric field, accelerating the argon ions to bombard a target under the action of the electric field, sputtering target atoms and generating secondary electrons; target material atoms are deposited into a film on a substrate, secondary electrons do rotary motion in an orthogonal magnetic field above a cathode, the distance from the electron motion to the anode is lengthened through the rotary motion, and more chances are provided for impacting argon atoms in the motion process to generate new argon ions and electrons; the secondary electrons after multiple times of impact are slowed down and finally get rid of the constraint of an orthogonal magnetic field to move to the anode, and the impact force to the film is small when the secondary electrons move to the anode due to the low capability, so that the damage to the film is reduced; the ion energy sputtered and deposited on the matrix is higher, and the cleaning effect is realized on the matrix, so that the adhesion between the film and the matrix is better, and the method has the advantages of high deposition rate, high yield and the like; in the migration process of the deposited atoms on the surface of the substrate, if the deposited atoms touch another adsorbed atom on the surface of the substrate, the deposited atoms are condensed into nuclei, other deposited particles are continuously gathered around the nuclei to ensure that the nuclei are continuously enlarged, the nuclei larger than the critical dimension are continuously enlarged to form stable islands, and a large number of stable islands are continuously added with the adsorbed atoms and finally are expanded into continuous films.

Detailed Description

Mixing ferric oxide, zinc oxide and copper oxide according to the mass ratio of 9: 2 to obtain mixed powder, mixing the mixed powder with deionized water according to the mass ratio of 1: 2, ball-milling for 3-4 h at the rotating speed of 300-400 r/min to obtain a mixture A, placing the mixture A in an oven at the temperature of 60-80 ℃ for drying to constant weight, cooling to room temperature, sieving with an 80-100-mesh sieve to obtain an abrasive A, placing the abrasive A in a muffle furnace, roasting for 1-2 h at the temperature of 1000-1050 ℃, and cooling to room temperature to obtain a roasted product A; mixing the roasted substance A, aluminum oxide, lanthanum oxide and deionized water according to the mass ratio of 10: 1: 2: 15, ball-milling for 5-6 h at the rotating speed of 400-500 r/min to obtain a mixture B, drying the mixture B in an oven at the temperature of 60-80 ℃ to constant weight, cooling to room temperature, sieving with an 80-100-mesh sieve to obtain an abrasive material B, placing the abrasive material B in a muffle furnace, carrying out heat preservation sintering at the temperature of 1100-1150 ℃ for 2-3 h, and cooling along with the furnace temperature to obtain the roasted substance B; placing the roasted material B in a mold with the diameter of 60mm and the thickness of 10mm, and pressing for 1-2 min under the pressure of 3-5 MPa to obtain a target material; mixing Al₂O₃Respectively ultrasonically cleaning the ceramic tube with acetone, absolute ethyl alcohol and deionized water for 10-15 min, naturally drying to obtain a matrix, pre-sputtering the matrix to a vacuum degree of 3.0 × 10^{- 4}Pa, using high-purity argon as sputtering gas, and pre-sputtering for 20-30 min to obtain a pre-sputtering matrix; sputtering the pre-sputtering substrate to form a film, wherein the sputtering power is 75-80W, the sputtering air pressure is 1.2-1.5 Pa, and then a semi-finished product is obtained, and the semi-finished product is heated at the temperatureAnnealing and preserving heat for 1-2 h at the temperature of 300-350 ℃, and cooling to room temperature to obtain the composite ceramic pipeline material for solar thermal power generation.