CN117344275A - High-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves and preparation method and application thereof - Google Patents

High-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves and preparation method and application thereof Download PDF

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Publication number
CN117344275A
CN117344275A CN202311218337.5A CN202311218337A CN117344275A CN 117344275 A CN117344275 A CN 117344275A CN 202311218337 A CN202311218337 A CN 202311218337A CN 117344275 A CN117344275 A CN 117344275A
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aln piezoelectric
aln
coating material
substrate
ultrasonic
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姜杨慧
杨兵
张俊
瓦西里
曾晓梅
张翔宇
陈燕鸣
黄家辉
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Wuhan University WHU
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Wuhan University WHU
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    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/25—Measuring force or stress, in general using wave or particle radiation, e.g. X-rays, microwaves, neutrons
    • G01L1/255—Measuring force or stress, in general using wave or particle radiation, e.g. X-rays, microwaves, neutrons using acoustic waves, or acoustic emission
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L5/00—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes
    • G01L5/24—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes for determining value of torque or twisting moment for tightening a nut or other member which is similarly stressed
    • G01L5/246—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes for determining value of torque or twisting moment for tightening a nut or other member which is similarly stressed using acoustic waves

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention provides a preparation method of a high temperature resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves, which comprises the following steps: forming an AlN piezoelectric functional layer on the surface of the substrate by adopting an Al target through magnetron sputtering; in the magnetron sputtering, the AlN piezoelectric functional layer grows in various orientations in the deposition process by controlling the volume ratio of argon to nitrogen, the temperature, the sputtering power, the deposition pressure and the target base distance. The AlN piezoelectric coating material prepared by the invention has good mechanical property, temperature resistance and corrosion resistance, ensures the AlN piezoelectric coating to have long-term stable service capability under high temperature and severe working conditions without a protective layer, reduces the failure possibility caused by factors such as corrosion and the like, and can realize accurate nondestructive measurement of the pretightening force of a bolt or detection and stress measurement of the defects of a steel matrix. The sputtering technology adopted by the invention is a general technology in industry, the industrial production batch is easy to realize, the processing efficiency is higher, and the production cost of factories can be greatly reduced.

Description

High-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves and preparation method and application thereof
Technical Field
The invention belongs to the technical field of coating materials, and particularly relates to a high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves and a preparation method thereof, and application of the AlN piezoelectric coating material in ultrasonic detection.
Background
The bolt fastener is the most widely used connecting mode at present due to the advantages of low cost, good interchangeability, convenient installation and disassembly and the like. Typical bolting forms include bolts, nuts and clamping members. When the bolt or nut is tightened, the bolt stretches and a preload is generated. Sufficient pretension is critical to ensure connection and fastening performance and to improve product reliability. Particularly, the working conditions faced by the aerospace equipment are complex and changeable, severe working conditions such as high temperature, high stress, long-time mutual friction and the like can be generally met, and the problems of pretightening force reduction, loosening, sliding, abnormal sound and the like of a bolt connection joint part can be frequently caused. Finally, the rigidity of the system is reduced, the structural integrity is damaged, the vibration is aggravated and the energy dissipation is increased, thereby affecting the working performance and the safety and reliability of the equipment.
The ultrasonic detection pretightening force technology has the advantages of high precision, good instantaneity, strong penetrating power and the like. The ultrasonic stress measuring method is to use ultrasonic probe and coupling agent to measure and paste piezoelectric ceramic plate onto the detected part. The film with the piezoelectric effect has the advantages of simple preparation method, high stability and wide applicability. The piezoelectric coating is directly deposited on the surface of the bolt, so that all adverse effects caused by a coupling agent or an adhesive can be avoided, and the measurement is quick and accurate. A great number of researches show that when the stress is detected by using a transverse wave and longitudinal wave combined method, except constants related to the performance and geometric shape of the material, only the longitudinal wave and transverse wave flight time and initial temperature of the bolt in an idle state are needed to be measured.
Piezoelectric materials that can be used to excite ultrasound at present are mainly ZnO and AlN, both of which are hexagonal wurtzite structures, whose properties for producing the piezoelectric effect depend entirely on their crystallographic orientation without polarization. ZnO does not have good high temperature resistance, and cannot be used under the working conditions of larger stress, long-term wear resistance and high temperature. The AlN piezoelectric material has good mechanical property, corrosion resistance and high temperature resistance, can grow on various substrates, has low requirement on epitaxial growth temperature, and is easier to control the stoichiometry and texture, so that an AlN coating with more excellent high temperature resistance and mechanical property can be selected as an ultrasonic excitation sound-electricity conversion layer.
Based on the method, the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves and the preparation method thereof are provided, and the high-temperature-resistant AlN piezoelectric coating material is applied to the manufacture of high-temperature-resistant intelligent bolts, has important significance for realizing accurate nondestructive measurement of pretightening force, and is a technical problem to be solved by researchers.
Disclosure of Invention
The invention aims to provide a preparation method of an AlN piezoelectric coating which has high mechanical property, corrosion resistance and high temperature resistance and can excite various ultrasonic waves.
The second purpose of the invention is to provide an AlN piezoelectric coating which has high mechanical property, corrosion resistance and high temperature resistance and can excite various ultrasonic waves.
The invention further aims to provide an application of the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves in ultrasonic detection.
One of the achievement purposes of the invention adopts the technical proposal that: the preparation method of the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves comprises the following steps: an Al target material is adopted, and an AlN piezoelectric functional layer is formed on the surface of a substrate through magnetron sputtering;
in the magnetron sputtering, the sputtering temperature is 60-250 ℃, and the target base distance is 40-80 mm; introducing mixed gas with the volume ratio of argon to nitrogen of 3:1-1:3 to the air pressure in the cavity of 0.6-4.0 Pa, the sputtering power of 500-900W and the sputtering time of 3-15 h.
In the preparation method, the AlN piezoelectric functional layer is prepared by utilizing radio frequency magnetron sputtering, the sputtering temperature is controlled to be 60-250 ℃, the temperature rise enables particles to have higher energy, and the particles can be ensured to have enough energy to migrate to the surface of a substrate within the temperature range so as to deposit an AlN coating; the volume ratio of argon to nitrogen is controlled, so that the atomic percentages of Al and N particles in the vacuum cavity can be controlled, the collision probability among the particles can be regulated, and the growth orientation of the coating can be regulated; the sputtering power of 500-900W is adopted, and under the sputtering power, the energy of particles can be adjusted, and the thickness of a prepared coating is controlled; the deposition air pressure (the pressure after the reaction gas is introduced into the vacuum chamber) is controlled to be P=0.6-4.0 Pa, the target base distance (the vertical distance between the target and the matrix) is 40-80 mm, and the average free path of Al and N particles can be regulated and controlled, so that AlN coatings with various oriented growth can be prepared in the deposition range. Under the preparation conditions, the AlN piezoelectric functional layer with high mechanical property, corrosion resistance and high temperature resistance can be prepared, and various ultrasonic waves can be excited.
In the invention, the substrate is selected from stainless steel, aluminum, hard alloy, high-speed steel, titanium and other substrates suitable for ultrasonic detection.
Further, in the magnetron sputtering, the higher the sputtering power is, the greater the ionization degree of argon is, and sputtered Al particles have higher kinetic energy to migrate to the surface of the substrate; the deposition time is prolonged, the thickness of the coating is increased, and the amplitude of ultrasonic signals excited by the coating is improved. Preferably, the sputtering power is 800-900W and the deposition time is 8-10 h.
Further, the diameter of the Al target is 100-160 mm, and the thickness of the Al target is 4-8 mm. In the invention, the diameter and thickness of the target material have a certain corresponding relation with the power of magnetron sputtering and the like. The application adopts the target material with larger diameter to be matched with higher sputtering power, so that more samples can be prepared simultaneously in the coating deposition process, the deposition efficiency is higher, the mass production is easy, and the popularization and the use are easier.
Further, the growth orientation of the AlN piezoelectric functional layer on the surface of the substrate comprises one or a combination of more of (002) diffraction crystal face, (100) diffraction crystal face, (101) diffraction crystal face and (102) diffraction crystal face.
Further, it has been found that in the present invention, by adjusting deposition parameters in the magnetron sputtering process, for example: the volume ratio of argon and nitrogen, the deposition air pressure and the target base distance can enable the AlN piezoelectric functional layer to present various growth orientations on the surface of the substrate, various ultrasonic waveforms can be excited, and then AlN piezoelectric coating materials capable of exciting different ultrasonic waves can be prepared according to detection requirements:
preferably, when the deposition temperature is 60-250 ℃, the sputtering power is 800-900W, and the deposition air pressure is 3.5-4.0 Pa and the volume ratio of argon to nitrogen is 1:1, the coating presents a (002) diffraction crystal face with high c-axis orientation, and the coating can emit obvious longitudinal waves under the condition of being excited;
preferably, when the volume ratio of the argon to the nitrogen is 1:3, the coating can emit obvious transverse waves under the condition of being excited;
preferably, the AlN piezoelectric functional layer exhibits typical multi-orientation growth including multi-orientation growth of (100) diffraction crystal plane, (002) diffraction crystal plane, (101) diffraction crystal plane and (102) diffraction crystal plane on the surface of the substrate when the deposition gas pressure is 0.6 to 2.8Pa and the volume ratio of argon gas to nitrogen gas is 3:1 to 1:2. Under the condition, the AlN piezoelectric coating material prepared by the invention can simultaneously emit the combined wave of the longitudinal wave and the transverse wave under the condition of being excited. A great number of researches show that when the stress is detected by using a transverse wave and longitudinal wave combined method, besides constants related to the performance and the geometric shape of the material, only the time of flight and the initial temperature of the longitudinal wave transverse wave in the idle state of the bolt are needed to be measured, and then the real-time load of the bolt can be obtained under the condition of not calibrating the original stress by simultaneously solving an eight-order polynomial.
Further, the preparation method comprises the following steps: and depositing a bonding layer on the surface of the substrate, depositing an AlN piezoelectric function layer on the surface of the bonding layer, and finally depositing an electrode layer on the surface of the AlN piezoelectric function layer. The bonding layer can increase the bonding force between the substrate and the coating, avoid the problems of cracking and falling of the coating in the long-term use process, and the electrode layer can provide an external electrode for the substrate (bolt or steel plate), so that two poles of the substrate can apply a stable voltage, and ultrasonic waves can be excited. The material of the bonding layer comprises Cr, and the electrode layer can be one of Cr, ti, ag, ag-Cr and silver powder-containing high-temperature glue.
Preferably, the preparation method of the invention can comprise the following steps:
s1, controlling the distance between a target material and a matrix to be 40-80 mm, and carrying out plasma etching on the surface of the matrix in a vacuum and argon environment at 60-250 ℃;
s2, depositing a Cr binding layer on the surface of the substrate subjected to plasma etching at the bias voltage of 50-250V under the pressure of 0.5-1 Pa;
s3, forming an AlN piezoelectric functional layer on the surface of the Cr binding layer by magnetron sputtering;
and S4, depositing an electrode layer on the surface of the AlN piezoelectric functional layer, wherein the electrode layer is selected from Cr, ti, ag, ag-Cr/silver powder-containing high-temperature glue, and thus the preparation of the AlN piezoelectric coating material is completed.
The second technical scheme adopted for realizing the purpose of the invention is as follows: there is provided a high temperature resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves, which is produced according to the production method according to one of the objects of the present invention.
The AlN piezoelectric coating material consists of a bonding layer, an AlN piezoelectric functional layer and an electrode layer. The AlN piezoelectric coating material prepared by the invention has high mechanical property, corrosion resistance and high temperature resistance, and can excite various ultrasonic waves. In some better embodiments, the high temperature-resistant AlN piezoelectric coating material is annealed for 200 hours at 800 ℃, the surface morphology and ultrasonic excitation performance of the high temperature-resistant AlN piezoelectric coating material are not changed, and the requirements of severe working conditions and long-term use in a high temperature environment can be met under the condition that a protective layer is not needed.
The third technical scheme adopted for realizing the purpose of the invention is as follows: the application of the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves is provided, and the high-temperature-resistant AlN piezoelectric coating material is used for exciting various ultrasonic waveforms for detecting the pretightening force of bolts or for detecting defects and measuring stress of steel plates, welding seams and steel pipes.
In some preferred embodiments, the substrate of the AlN piezoelectric coating material is an intelligent bolt, and according to the preparation method provided by the invention, a bonding layer, an AlN piezoelectric functional layer and an electrode layer are sequentially deposited on the surface of the intelligent bolt. According to the specific requirement of bolt pretightening force measurement, relevant parameters in the preparation method of the AlN piezoelectric coating material are adjusted in a targeted manner, so that the intelligent bolt with the piezoelectric coating material on the surface can excite different waveforms (longitudinal waves, transverse waves or longitudinal and transverse waves). The characteristic can simplify the calculation step of the bolt pretightening force, improve the measurement accuracy, and the AlN piezoelectric coating of the intelligent bolt has the advantages of high mechanical property, corrosion resistance, high temperature resistance and the like, can widen the working temperature range, improve the working performance under severe working conditions, prolong the service life of the intelligent bolt,
compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the high-temperature-resistant AlN piezoelectric coating capable of exciting various ultrasonic waves, provided by the invention, the AlN piezoelectric coating is prepared by utilizing radio frequency magnetron sputtering, and piezoelectric coating materials capable of exciting different waveforms simultaneously can be prepared by adjusting different deposition temperatures, sputtering power, deposition air pressure, flow ratio of argon and nitrogen and the distance between a target and a substrate, and the pretightening force of a bolt can be accurately measured. Besides, the AlN piezoelectric coating is used as a hard coating, is different from the ZnO piezoelectric coating, has high hardness, high wear resistance and high corrosion resistance, does not need to additionally deposit a protective layer, has high temperature resistance, can be used for a long time at 800 ℃, can be used for a long time under severe working conditions, and is simple to prepare and high in working efficiency.
(2) The AlN piezoelectric coating prepared by the invention forms an AlN piezoelectric functional layer through magnetron sputtering, and has the following advantages: firstly, the AlN coating with high piezoelectric coefficient, high electromechanical coupling coefficient and low epitaxial growth temperature is utilized, so that the AlN coating can be applied to various materials with larger acoustic attenuation coefficients; secondly, the AlN coating is directly deposited on the surface of the bolt to be used as an acoustic-electric conversion layer for exciting ultrasonic, so that a nondestructive detection technology can be realized; thirdly, the AlN piezoelectric coating has high hardness, and the hardness is more than 15GPa; fourth, the AlN piezoelectric coating of the present invention has high wear resistance, can achieve extremely low wear rate, and exhibits excellent wear resistance in wear tests; fifth, the AlN piezoelectric coating of the invention has high bonding strength, and the bonding strength can be more than 10MPa; sixthly, the AlN piezoelectric coating has high corrosion resistance, the neutral salt spray corrosion resistance time is more than 1000 hours, the alkali corrosion resistance performance is excellent, and the AlN piezoelectric coating can be soaked in a 5% NaOH solution for a long time and still can be normally used; seventh, alN coating prepared in the invention has excellent temperature resistance, can be used between-196 ℃ and 700 ℃; eighth, the AlN piezoelectric coating prepared in the invention has high accuracy, and the accuracy can be less than 5%; ninth, the AlN piezoelectric coating capable of simultaneously exciting ultrasonic longitudinal waves and ultrasonic longitudinal-transverse waves can be prepared by adjusting the deposition temperature, the sputtering power, the deposition air pressure, the flow ratio of argon and nitrogen and the distance between the target and the substrate, and the preparation method is simple and feasible, has wide adaptability and can also provide important value for the field of novel ultrasonic transducers.
(3) The AlN piezoelectric coating prepared by the method has high hardness, high wear resistance, high binding force, high corrosion resistance and excellent temperature resistance, can simultaneously excite ultrasonic longitudinal-transverse waves, can measure the pretightening force of a bolt with high precision, can be used for defect detection and stress measurement of a steel plate, a welding line and a steel pipe, can ensure long-term stable work of the piezoelectric coating on the surfaces of various alloy bolts, and reduces the possibility of failure. Meanwhile, the preparation technology and equipment are relatively close to those of the existing industrial equipment, industrial production is easy to realize in batches, the processing efficiency is high, the production cost of factories can be greatly reduced, and the method has wide popularization and application prospects.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing an AlN piezoelectric coating material used in the embodiment of the invention;
FIG. 2 is an XRD pattern of a thin film prepared at different deposition powers according to example 1 of the present invention;
FIG. 3 is a graph showing ultrasonic signals of AlN thin film excitation prepared at different deposition temperatures in example 2 of the present invention;
FIG. 4 is a graph showing ultrasonic signals of AlN film excitation at different sputtering pressures in example 3 of the present invention;
FIG. 5 is a graph showing ultrasonic signals of AlN thin film excitation at different argon-nitrogen ratios in example 4 of the present invention;
FIG. 6 is a graph of ultrasonic signals of AlN thin film excitation prepared at different target pitches in example 5 of the present invention;
FIG. 7 is a graph showing ultrasonic signals of AlN thin film excitation prepared in example 6 of the present invention at different deposition times;
FIG. 8 is a topography of the surface and cross section of an AlN thin film prepared in example 7 of the present invention after heat treatment annealing at 600 ℃, 700 ℃, 800 ℃ and 900 ℃, respectively;
FIG. 9 is a graph of ultrasonic echo signals after heat treatment of AlN thin film prepared on stainless steel substrate at 600-800 deg.C annealing temperature for 1h in example 7 of the present invention;
FIG. 10 is a graph showing the surface morphology of an AlN thin film prepared under the condition of example 7 of the present invention, wherein the AlN thin film is annealed at 800℃for 1h, 5h, 20h, 50h, 100h, 200h, respectively;
FIG. 11 is an ultrasonic echo signal diagram of an AlN thin film prepared on a substrate of a bolt at an annealing temperature of 800 ℃ under the deposition condition of an AlN piezoelectric functional layer of example 7 after heat treatment for 1-200 hours;
wherein 1-radio frequency magnetron sputtering (RF); 2-Al target material; 3-bolt samples; 4-an etching source; 5-sample holder; 6-a workpiece frame; 7-a heater; 8, an extraction opening; 9-furnace door.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
FIG. 1 shows an apparatus for use in the present invention, wherein the vacuum chamber of the apparatus is defined by the furnace walls and has a size of 400X400 mm. The vacuum chamber is provided with an extraction opening 8, and the vacuum pumping unit is used for vacuumizing the vacuum chamber through the extraction opening 8. The upper two corners of the vacuum chamber are provided with heaters 7, the heating power is 25 kilowatts, and the heating efficiency is improved; the lower two corners of the vacuum chamber are etching sources 4, so that impurities on the surface of the substrate can be removed, and the surface of the substrate is ensured to be clean. The Al target 2 is arranged on the furnace wall and is connected with a radio frequency magnetron sputtering (RF) 1, the sputtering power can be adjusted, the back of the Al target 2 faces the furnace door 9, the front of the Al target is a sample 3, the sample is placed on a sample frame 5, and the sample frame is arranged on a workpiece frame 6. This arrangement greatly increases the plasma density in the vacuum chamber and the workpiece is completely immersed in the plasma. The deposition rate, hardness and adhesive force of the coating are greatly improved. The target structure is optimized, so that the magnetic field distribution is more uniform, the magnetron sputtering target surface is uniformly etched, and the uniformity of the coating is improved.
The general preparation method of the AlN piezoelectric coating material with high temperature resistance, which can excite various ultrasonic waves, provided by the embodiment of the invention comprises the following steps:
controlling the distance between the target and the matrix to be 40-80 mm, and vacuumizing at 60-250 ℃ to be no more than 5 multiplied by 10 - 3 Pa, introducing 50-100sccm argon (purity 99.99%), starting bias voltage and arc power supply, carrying out plasma etching on the substrate under the conditions of-100 to-150V, duty ratio of 40-80%, air pressure of 0.5-1 Pa and current of 70-90A, removing impurities attached to the surface of the substrate, and improving the binding force of a film layer and the substrate;
after etching, vacuumizing to not more than 5×10 -3 Pa, controlling the position of the substrate to be opposite to the center of the target, introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is from 3:1 to 1:3, the air pressure in the cavity is 0.6 to 4.0Pa, starting a radio frequency power supply, the sputtering power is 500 to 900W respectively, and the sputtering time is 3 to 15 hours; after the AlN piezoelectric coating is prepared, naturally cooling to room temperature, and obtaining the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves on the surface of the substrate.
The invention will be further illustrated, but is not limited, by the following examples. The main parameters and variables involved in the preparation of the AlN piezoelectric coating in each example of the present invention are shown in table 1 below.
TABLE 1
The substrate in each embodiment is a Si substrate, a stainless steel substrate or a bolt, and the target is a pure Al (purity 99.9999%) target.
Example 1
Control target and substrateThe distance between the two is 55mm, and the vacuum is pumped at 100 ℃ to be no more than 5 multiplied by 10 -3 Pa, introducing 50-100sccm argon (purity 99.99%), starting bias voltage and arc power supply, carrying out plasma etching on the substrate under the conditions of-100 to-150V, duty ratio of 40-80%, air pressure of 0.5-1 Pa and current of 70-90A, removing impurities attached to the surface of the substrate, and improving the binding force of the film layer and the substrate.
After etching, vacuumizing to not more than 5×10 -3 Pa, controlling the position of the matrix to be opposite to the center of the target, and introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is 1:1, starting a radio frequency power supply until the air pressure in the cavity is 3.5Pa, wherein the sputtering power is 500W, 600W, 700W, 800W and 900W respectively, and the sputtering time is 8h; after the AlN piezoelectric coating is prepared, naturally cooling to room temperature, and obtaining the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves on the surface of the substrate.
Example 2
Controlling the distance between the target and the matrix to be 55mm, and vacuumizing to be not more than 5×10 under the conditions that the temperature is 60 ℃, 100 ℃, 150 ℃, 200 ℃ and 250 ℃ respectively -3 Pa, introducing 50-100sccm argon (purity 99.99%), starting bias voltage and arc power supply, carrying out plasma etching on the substrate under the conditions of-100 to-150V, duty ratio of 40-80%, air pressure of 0.5-1 Pa and current of 70-90A, removing impurities attached to the surface of the substrate, and improving the binding force of the film layer and the substrate.
After etching, vacuumizing to not more than 5×10 -3 Pa, controlling the position of the matrix to be opposite to the center of the target, and introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is 1:1, starting a radio frequency power supply until the air pressure in the cavity is 3.5Pa, and sputtering at 900W for 8 hours; after the AlN piezoelectric coating is prepared, naturally cooling to room temperature, and obtaining the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves on the surface of the substrate.
Example 3
Controlling the distance between the target and the matrix to be 55mm, and vacuumizing to be not more than 5 x 10 at 100 DEG C -3 Pa, introducing 50% to the contrary100sccm argon (purity 99.99%), turning on bias voltage and arc power supply, and performing plasma etching on the substrate under the conditions of-100 to-150V, duty ratio 40-80%, air pressure 0.5-1 Pa and current 70-90A to remove impurities attached to the surface of the substrate and improve the binding force of the film layer and the substrate.
After etching, vacuumizing to not more than 5×10 -3 Pa, controlling the position of the matrix to be opposite to the center of the target, and introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is 1:1, starting a radio frequency power supply until the air pressure in the cavity is respectively 0.6Pa, 1.2Pa, 2.0Pa, 2.6Pa and 3.5Pa, wherein the sputtering power is 900W, and the sputtering time is 8h; after the AlN piezoelectric coating is prepared, naturally cooling to room temperature, and obtaining the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves on the surface of the substrate.
Example 4
Controlling the distance between the target and the matrix to be 55mm, and vacuumizing to be not more than 5 x 10 at 100 DEG C -3 Pa, introducing 50-100sccm argon (purity 99.99%), starting bias voltage and arc power supply, carrying out plasma etching on the substrate under the conditions of-100 to-150V, duty ratio of 40-80%, air pressure of 0.5-1 Pa and current of 70-90A, removing impurities attached to the surface of the substrate, and improving the binding force of the film layer and the substrate.
After etching, vacuumizing to not more than 5×10 -3 Pa, controlling the position of the substrate to be opposite to the center of the target, introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is 3/1, 2/1, 1/2 and 1/3 respectively, until the air pressure in the cavity is 2.8Pa, 1.6Pa, 0.6Pa, 1.0Pa and 1.4Pa respectively, starting a radio frequency power supply, the sputtering power is 900W, and the sputtering time is 8h; after the AlN piezoelectric coating is prepared, naturally cooling to room temperature, and obtaining the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves on the surface of the substrate.
Example 5
The distances between the target and the matrix are controlled to be 55mm, 60mm, 65mm, 70mm and 75mm respectively, and the vacuum is pumped at 100 ℃ to be no more than 5 x 10 -3 Pa, introducing 50-100sccm argon (purity 99.99%), and starting biasAnd the voltage and arc power supply performs plasma etching on the substrate under the conditions of-100 to-150V, duty ratio of 40-80%, air pressure of 0.5-1 Pa and current of 70-90A, so as to remove impurities attached to the surface of the substrate and improve the binding force of the film layer and the substrate.
After etching, vacuumizing to not more than 5×10 -3 Pa, controlling the position of the matrix to be opposite to the center of the target, and introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is from 1:1, starting a radio frequency power supply until the air pressure in the cavity is 0.6Pa, wherein the sputtering power is 900W, and the sputtering time is 8h; after the AlN piezoelectric coating is prepared, naturally cooling to room temperature, and obtaining the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves on the surface of the substrate.
Example 6
Controlling the distance between the target and the matrix to be 60mm, and vacuumizing to be not more than 5 x 10 at 100 DEG C -3 Pa, introducing 50-100sccm argon (purity 99.99%), starting bias voltage and arc power supply, carrying out plasma etching on the substrate under the conditions of-100 to-150V, duty ratio of 40-80%, air pressure of 0.5-1 Pa and current of 70-90A, removing impurities attached to the surface of the substrate, and improving the binding force of the film layer and the substrate.
After etching, vacuumizing to not more than 5×10 -3 Pa, controlling the position of the matrix to be opposite to the center of the target, and introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is from 1:1, starting a radio frequency power supply until the air pressure in the cavity is 3.6Pa, and sputtering at 900W for 4h, 6h, 8h and 10h respectively; after the AlN piezoelectric coating is prepared, naturally cooling to room temperature, and obtaining the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves on the surface of the substrate.
Example 7
Controlling the distance between the target and the matrix to be 55mm, and vacuumizing at 250 ℃ to be no more than 5 x 10 -3 Pa, introducing 50-100sccm argon (purity 99.99%), turning on bias voltage and arc power supply, performing plasma etching on the substrate under the conditions of-100 to-150V, duty ratio 40-80%, air pressure 0.5-1 Pa and current 70-90A to remove the surface of the substrateThe surface-attached impurities improve the binding force of the film layer and the matrix.
After etching, vacuumizing to not more than 5×10 -3 Pa, controlling the position of the matrix to be opposite to the center of the target, and introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is 1:1, starting a radio frequency power supply until the air pressure in the cavity is 3.5Pa, and sputtering at 900W for 8 hours; after the AlN piezoelectric coating is prepared, naturally cooling to room temperature, and obtaining the high-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves on the surface of the substrate.
Performance testing
(one) Effect of different sputter powers on film growth orientation
FIG. 2 shows XRD patterns of films prepared under different deposition powers in example 1 of the present invention, and it can be seen from the graph that, under the precondition that the deposition pressure is 3.5Pa, the flow ratio of argon to nitrogen is 1:1, and the target base distance is 55mm, the position of diffraction peak of AlN film is not changed along with the change of sputtering power, and the c-axis preferred orientation growth of diffraction peak of (002) appears at about 35.5 degrees. With the increase of the sputtering power, the diffraction peak intensity and the half-width of the thin film show a trend of increasing and then decreasing, when the sputtering power is 800W, the diffraction peak intensity reaches the maximum, and when the sputtering power is 900W, the half-width of the thin film is minimum, because the greater the sputtering power, the greater the ionization degree of argon gas, the higher the kinetic energy of sputtered Al particles migrates to the surface of the substrate, and the more remarkable c-axis preferential growth is shown.
(II) influence of different sputtering temperatures on film growth orientation
FIG. 3 shows ultrasonic signals of AlN thin films prepared at different deposition temperatures according to example 2 of the present invention. As can be seen from the graph, on the premise that the deposition air pressure is 3.5Pa, the flow ratio of argon to nitrogen is 1:1, the target base distance is 55mm, and the sputtering power is 900W, the AlN piezoelectric film prepared under the condition of different deposition temperatures can excite ultrasonic longitudinal waves, because the prepared AlN piezoelectric film shows c-axis preferred orientation growth, the grown structure is vertical to the surface of the substrate, and particles easily vibrate in the direction parallel to the propagation direction of the ultrasonic waves, so that ultrasonic Longitudinal Waves (LW) are excited.
(III) ultrasonic signals excited by AlN films under different sputtering air pressures
FIG. 4 shows ultrasonic signals excited by AlN thin films under different sputtering pressures in the embodiment 3 of the invention, two ultrasonic types of ultrasonic longitudinal waves and ultrasonic transverse waves can be seen from the ultrasonic signals, on the premise that the sputtering power and the sputtering time are kept unchanged, the flow ratio of argon to nitrogen is 1:1, the target base distance is unchanged, when the deposition pressure is 3.5Pa, the ultrasonic waveform excited is the ultrasonic longitudinal waves, and along with the reduction of the sputtering pressure, the ultrasonic waves excited by the thin films are longitudinal-transverse mixed waves, which are related to the growth structure and the morphology of the thin films. When the sputtering air pressure is 3.5Pa, the growth of the film is (002) oriented growth, which is expressed as highly preferred growth orientation, and the appearance is a columnar crystal structure which grows perpendicular to the substrate, so that the excited ultrasonic waveform is ultrasonic longitudinal wave. As the deposition air pressure is reduced, the growth orientation of the film is changed from (002) growth orientation to (100), (002) and (101) multi-orientation growth, and the growth morphology of the film is changed from columnar crystal growth perpendicular to the substrate to growth inclined to the substrate, so that the excited ultrasonic wave is also changed from ultrasonic longitudinal wave to ultrasonic longitudinal-transverse mixed wave.
(IV) ultrasonic signals excited by AlN films under different argon-nitrogen ratios
FIG. 5 shows ultrasonic signals of AlN thin film excitation in different argon-nitrogen ratios in example 4 of the invention, and it can be seen from the figure that under the condition that the target base distance is 55mm and the deposition air pressure is 0.6-2.8 Pa, the excited ultrasonic waves are of two ultrasonic wave types of longitudinal wave and transverse wave, and from the ultrasonic signal diagram, ultrasonic longitudinal-transverse waves can be excited in the range of 3:1-1:2 of the argon-nitrogen ratio, which is related to the growth orientation of the thin film, and the growth orientation of the thin film can be excited in the range of the argon-nitrogen ratio as the multi-orientation growth structure of (100), (002), (101) and (102). At an argon-nitrogen ratio of 1:3, the film showed significant growth of robustly columnar crystals, and the structure can excite significant transverse waves (SW), which corresponds to the cross-sectional morphology of the film.
(V) ultrasonic signals excited by AlN thin films prepared under different target base distances
FIG. 6 shows ultrasonic signals excited by AlN thin films prepared under different target pitches according to the embodiment 5 of the invention, from which the ultrasonic waves excited by the AlN thin films can be of two ultrasonic types of longitudinal waves and transverse waves under the conditions that the deposition air pressure is 0.6Pa and the flow ratio of argon to nitrogen is 1:1.
(six) ultrasonic signals excited by AlN thin films prepared at different times
FIG. 7 shows ultrasonic signals excited by AlN thin films prepared in different time periods in the embodiment 6 of the invention, and the ultrasonic signals excited on the premise that the deposition pressure is 3.6Pa, the flow ratio of argon to nitrogen is 1:1 and the target base distance is 60mm is unchanged are all ultrasonic longitudinal wave signals. Along with the increase of the deposition time, the amplitude of ultrasonic signals excited by the coating is continuously increased, and the c-axis preferred orientation of the coating is better along with the increase of the deposition time by combining an X-ray diffraction spectrum and a scanning electron microscope image, so that the capability of exciting ultrasonic signals of the coating is enhanced, and the best is achieved in 10 hours.
Testing the high temperature resistance of AlN film
The AlN film prepared in the embodiment 7 is subjected to a high-temperature annealing experiment, the annealing experiment is carried out in a muffle furnace with the model of XMT-8000, the annealing temperature of the AlN film is 400-900 ℃, the heating rate is 5 ℃/min, the heat preservation time is 1-200h, and after the annealing experiment is finished, the sample is cooled to room temperature along with the furnace and then taken out.
FIG. 8 is a graph showing the surface and cross section of an AlN film obtained in example 7 of the present invention after annealing at 600, 700, 800 and 900. DegreeC, respectively, and the surface of the AlN film is dense, free of cracks and large particles, and has obvious grain arrangement, and obvious grain boundaries can be seen from the graph of the annealed surface morphology. The surface morphology of the AlN film is not changed when the annealing temperature is 600-800 ℃, and the AlN film is in a similar grain size and grain state when not annealed, which indicates that the prepared AlN film is subjected to heat treatment at the temperature of 800 ℃ and cannot damage the morphology of the film to change the surface morphology. As the annealing temperature increases, the surface morphology is clearly seen when the annealing temperature reaches 900 ℃. The short-time annealing at 800 ℃ is shown, the appearance of the AlN film is not changed, and the film can still be normally used.
FIG. 9 is a graph showing ultrasonic echo signals of an AlN thin film prepared on a stainless steel substrate according to the invention after heat treatment for 1h at an annealing temperature of 600-800. DegreeC. It can be seen from the graph that the increase of the annealing temperature does not change the amplitude and position of the ultrasonic signals excited by the AlN thin film, the heat treatment for 1h at an annealing temperature of 800. DegreeC does not change the waveform and intensity of ultrasonic waves excited by the AlN thin film, and ultrasonic longitudinal waves can be excited after heat treatment because the (002) growth orientation of the AlN thin film is not changed in the annealing temperature range and ultrasonic longitudinal waves can be excited in the growth orientation.
The ultrasonic echo signal of the AlN film prepared on the substrate of the bolt after heat treatment for 1h at the annealing temperature of 600-800 ℃ is shown in a graph (b), and the length of the bolt is far longer than the thickness of the stainless steel plate, so that the excited ultrasonic signal can be more obviously distinguished, and the AlN film prepared under the deposition condition has good piezoelectric performance on the bolt, can excite obvious four-time bottom ultrasonic echo signals, and the amplitude of the echo signal is gradually reduced. According to the flight time of ultrasonic waves in the bolt, 8.09 mu s is taken, the flight distance is 24mm of the length of the bolt, the propagation speed of the AlN film on the stainless steel bolt is 5858m/s, and the fact that the excited waveform is still ultrasonic longitudinal wave and the waveform excited on the stainless steel sheet is consistent is shown. As can be seen from the graph (b), the position of the AlN film on the bolt excited by the ultrasonic signal is not changed when the annealing temperature is increased, and the AlN film on the bolt can still excite ultrasonic longitudinal waves after being thermally treated for 1h in the annealing temperature range of 800 ℃. The amplitudes of the ultrasonic primary and secondary echo signals of the bolts subjected to heat treatment at different annealing temperatures are shown as a graph (c), and the amplitude of the excited ultrasonic echo signals of the bolts shows a trend of increasing and then decreasing, because the particle energy in the AlN film is increased, the capability of migrating and rearranging to the (002) direction is enhanced due to the increase of the temperature, and the reason of better c-axis oriented growth is shown. Since the (002) growth orientation of the AlN film is not changed, ultrasonic longitudinal waves can be excited after annealing at different temperatures. The AlN thin film prepared on the bolt was subjected to the decay rate calculation after 1h annealing at different annealing temperatures, and the graph was shown in the graph (d). As can be seen from the graph, the decay rate is at least 49.7% after annealing at 700 ℃, which means that the AlN film heat-treated at this temperature has excellent temperature resistance and can maintain a low decay rate.
FIG. 10 shows that the AlN thin film prepared under the condition of the embodiment 7 of the invention is annealed for 1h, 5h, 20h, 50h, 100h and 200h respectively under the condition of 800 ℃, the surface morphology of the AlN thin film after annealing is shown in FIG. 10, and the surface of the AlN thin film is uniform, the thin film shows obvious grain arrangement, and the surface is clean and free of large particles as can be seen from the surface morphology graph after annealing. The annealing time is from 1h to 200h, the surface morphology of the AlN film is not changed, the crystal grain size and the crystal grain state similar to those of the AlN film which is not annealed are shown, the prepared AlN film is annealed for 200h at the temperature of 800 ℃ by heat treatment, the surface morphology of the film is not damaged, the surface morphology of the film is not changed, the prepared AlN film is annealed for a long time at the temperature of 800 ℃, the morphology of the AlN film is not changed, the film can still be normally used, and the AlN film has good long-term high temperature resistance.
Application example
The application example adopts a stainless steel bolt with the length of 24mm as a matrix, and an AlN piezoelectric coating material is deposited on the surface of the stainless steel bolt, so that the preparation of the high-temperature-resistant intelligent bolt capable of exciting various ultrasonic waves is realized. The preparation method of the intelligent bolt comprises the following steps:
step 1: controlling the distance between the target and the matrix to be 50-80 mm, and vacuumizing at room temperature-250 ℃ to be no more than 5 multiplied by 10 -3 Pa, introducing 50-100sccm argon (purity 99.99%), turning on bias voltage and arc power supply, and applying a duty ratio of 40-80% at-100 to-150V, air pressure of 0.5-1 Pa, and current of 70-90A to the substratePerforming plasma etching to remove impurities attached to the surface of the substrate and improve the binding force between the film and the substrate;
step 2: after etching, preparing a bonding layer Cr on the bolt substrate under the condition of 0.5-1 Pa and 50-250V bias voltage, so that the internal stress can be eliminated, the bonding force between the coating and the substrate can be increased, and the thickness of the bonding layer is about 500nm;
step 3: after the preparation of the bonding layer, the bonding layer is vacuumized to 3 multiplied by 10 at the room temperature to 250 DEG C -3 Pa～7×10 -3 Pa, controlling the position of the substrate to be opposite to the center of the target, introducing mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%), wherein the flow ratio of the argon to the nitrogen is from 3:1 to 1:3, the air pressure in the cavity is 0.6Pa to 4Pa, starting a radio frequency power supply, the sputtering power is 500W to 900W, and the sputtering time is 3 h to 10h, so as to form the AlN piezoelectric functional layer;
step 4: after the AlN piezoelectric functional layer is prepared, depositing an electrode layer under the conditions of 0.25-1 Pa, 0-100V bias and 0-80A current, wherein the electrode layer is selected from one of Ag, ag-Cr, ti and high-temperature glue containing silver powder; after the preparation is completed, naturally cooling to room temperature, and obtaining the high temperature-resistant intelligent bolt capable of exciting various ultrasonic waves.
FIG. 11 is an ultrasonic echo signal graph after heat treatment of an AlN thin film prepared on a substrate of a bolt at an annealing temperature of 800℃for 1-200 hours using the deposition conditions of the AlN piezoelectric functional layer of example 7. It can be seen that the AlN film excites obvious four times of bottom ultrasonic echo signals on the bolt, the amplitude of the echo signals is gradually reduced, and the excited ultrasonic waveform is ultrasonic longitudinal wave. After annealing for 200 hours at 800 ℃, the amplitude of the ultrasonic echo signal of the bolt is weaker, but the amplitude of the ultrasonic echo signal can be amplified by adjusting the gain of the ultrasonic measuring equipment. Therefore, the AlN film prepared in the method has good temperature resistance, can still excite ultrasonic waves after being annealed for 200 hours at the high temperature of 800 ℃, and can be used stably for a long time.
The above application example uses a bolt substrate as an example, and the preparation method of the AlN piezoelectric coating material is also applicable to substrates such as stainless steel, aluminum, cemented carbide, high-speed steel, titanium, and the like, which are not limited herein.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings of the present invention, which are intended to be included within the scope of the present invention.

Claims (10)

1. A preparation method of a high-temperature-resistant AlN piezoelectric coating material capable of exciting a plurality of ultrasonic waves is characterized by comprising the following steps of: an Al target material is adopted, and an AlN piezoelectric functional layer is formed on the surface of a substrate through magnetron sputtering;
in the magnetron sputtering, the sputtering temperature is 60-250 ℃, the target base distance is 40-80 mm, the mixed gas of argon and nitrogen with the volume ratio of 3:1-1:3 is introduced to the air pressure in the cavity of 0.6-4.0 Pa, the sputtering power is 500-900W, and the sputtering time is 3-15 h.
2. The method according to claim 1, wherein in the magnetron sputtering, the sputtering power is 800 to 900W and the deposition time is 8 to 10 hours.
3. The method according to claim 1, wherein the Al target has a diameter of 100 to 160mm and a thickness of 4 to 8mm.
4. The method according to claim 1, wherein the growth orientation of the AlN piezoelectric functional layer on the surface of the substrate includes one or a combination of (002) diffraction crystal plane, (100) diffraction crystal plane, (101) diffraction crystal plane, and (102) diffraction crystal plane.
5. The preparation method according to claim 1, wherein a bonding layer is deposited on the surface of the substrate, an AlN piezoelectric function layer is deposited on the surface of the bonding layer, and an electrode layer is deposited on the surface of the AlN piezoelectric function layer.
6. The method of manufacturing according to claim 1, comprising the steps of:
s1, controlling the distance between a target material and a matrix to be 40-80 mm, and carrying out plasma etching on the surface of the matrix in a vacuum and argon environment at 60-250 ℃;
s2, depositing a Cr binding layer on the surface of the substrate subjected to plasma etching at the bias voltage of 50-250V under the pressure of 0.5-1 Pa;
s3, forming an AlN piezoelectric functional layer on the surface of the Cr binding layer by magnetron sputtering;
and S4, depositing an electrode layer on the surface of the AlN piezoelectric functional layer to finish the preparation of the AlN piezoelectric coating material.
7. The method according to claim 6, wherein in the step S3, the electrode layer is selected from one of Cr, ti, ag, ag-Cr and silver powder-containing high-temperature paste.
8. A high temperature-resistant AlN piezoelectric coating material capable of exciting a plurality of ultrasonic waves, characterized by being produced according to the production method according to any one of claims 1 to 7, the AlN piezoelectric coating material being composed of a bonding layer, an AlN piezoelectric functional layer and an electrode layer.
9. The high temperature resistant AlN piezoelectric coating material capable of exciting a plurality of ultrasonic waves according to claim 8, wherein the high temperature resistant AlN piezoelectric coating material is annealed at 800 ℃ for 200 hours with its surface morphology unchanged and still maintains the ultrasonic excitation performance.
10. Use of a high temperature resistant AlN piezoelectric coating material according to claim 8 or 9, wherein the high temperature resistant AlN piezoelectric coating material excites a plurality of ultrasonic waveforms for pretension detection of bolts or for defect detection and stress measurement of steel plates, welds, steel pipes.
CN202311218337.5A 2023-09-19 2023-09-19 High-temperature-resistant AlN piezoelectric coating material capable of exciting various ultrasonic waves and preparation method and application thereof Pending CN117344275A (en)

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