Ti surface K0. 65Na0. 35NbO3 piezoelectric ceramic active coating material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of medical titanium metal surface electroactive coatings, and provides a Ti surface K0. 65Na0. 35NbO3 piezoelectric ceramic active coating material as well as a preparation method and application thereof, and the preparation method comprises the following steps: preparing Ti / K0. 65Na0. 35NbO3 composite powder by a ball milling method; ti / K < 0.65 > Na < 0.35 > NbO3 composite powder and K < 0.65 > Na < 0.35 > NbO3 powder are sequentially laid on a Ti matrix subjected to surface pretreatment, a spark plasma sintering body is prepared through spark plasma sintering, and the Ti surface K < 0.65 > Na < 0.35 > NbO3 piezoelectric ceramic active coating material is prepared through annealing treatment of the spark plasma sintering body. The Ti substrate and the K0. 65Na0. 35NbO3 layer are stably and firmly combined through the Ti / K0. 65Na0. 35NbO3 composite gradient connecting layer, the Ti surface K0. 65Na0. 35NbO3 piezoelectric ceramic active coating material with excellent piezoelectric ferroelectric performance, dielectric performance and binding performance is achieved, and accurate regulation and control of the performance of the Ti surface K0. 65Na0. 35NbO3 piezoelectric ceramic active coating material can be achieved.

Description

Technical Field

[0001] This invention relates to the field of electroactive coating technology for medical titanium metal surfaces, and particularly to a K-coating for Ti surfaces. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating materials, their preparation methods, and applications. Background Technology

[0002] Titanium is widely used as a biomedical material (such as implantable restorative materials in orthopedics and dentistry) due to its good corrosion resistance, excellent comprehensive mechanical properties, and good biocompatibility. However, titanium is susceptible to bacterial infection and corrosion during application, and its surface does not exhibit biological activity, making it difficult to interact with human tissue cells, thus diminishing its biomedical value.

[0003] Sodium potassium niobate piezoelectric ceramics, as a type of piezoelectric material with electrical signal responsiveness, are widely considered a promising material for human implants due to their advantages such as being lead-free, non-toxic, and biocompatible. To realize its application in human implants, it is usually prepared as a coating on the implant surface. Currently, the mainstream coating preparation method is thermal spraying. However, the high temperature during thermal spraying can easily cause the volatilization of volatile elements such as K and Na, affecting the original piezoelectric and ferroelectric properties of the material. The coating produced by spraying relies mainly on mechanical interlocking with the substrate, and the bonding strength is usually lower than that of metallurgical bonding. Furthermore, the coating often contains pores and microcracks, affecting its corrosion resistance, sealing, and fatigue performance. The spraying process may generate dust, noise, and heat radiation, posing potential hazards to operators and the environment, requiring appropriate environmental protection and safety facilities. At the same time, thermal spraying is difficult to apply to implants with complex, microscopic surfaces, such as dental implants, which also limits its application in the field of dental implant materials.

[0004] Therefore, how to provide a method that combines good piezoelectric and ferroelectric properties, bonding strength, and the ability to prepare coatings on complex and tiny implant surfaces has become an urgent technical problem to be solved. Summary of the Invention

[0005] In view of this, in order to overcome the shortcomings of the prior art, the present invention aims to provide a Ti surface K 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating materials, their preparation methods, and applications.

[0006] According to a first aspect of the present invention, a Ti surface K is provided. 0.65 Na 0.35 A method for preparing NbO3 piezoelectric ceramic active coating materials, comprising: preparing Ti / K by ball milling. 0.65 Na 0.35NbO3 composite powder was sequentially layered onto a surface-pretreated Ti matrix using Ti / K composite powder. 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 NbO3 powder was used to prepare a spark plasma sintered body, and the spark plasma sintered body was then annealed to obtain the K on the Ti surface. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material.

[0007] Optionally, the Ti surface K of the present invention 0.65 Na 0.35 A method for preparing NbO3 piezoelectric ceramic active coating materials, using 1-3 parts by weight of K 0.65 Na 0.35 Using NbO3 and 7-9 parts by weight of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min. 0.65 Na 0.35 NbO3 composite powder.

[0008] Optionally, the Ti surface K of the present invention 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material involves surface pretreatment of the Ti substrate as follows: the Ti substrate surface is sprayed with abrasive, and then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 min respectively, followed by drying at 40℃.

[0009] Optionally, the Ti surface K of the present invention 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material involves spraying white corundum abrasive with a basic particle size of 100 mesh onto the Ti substrate surface at a spraying distance of 100 mm for 20 seconds.

[0010] Optionally, the Ti surface K of the present invention 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material involves using 0.1g of Ti / K 0.65 Na 0.35 NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

[0011] Optionally, the Ti surface K of the present invention0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material, the spark plasma sintered body is prepared in the following manner: A Ti / K... 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace.

[0012] Optionally, the Ti surface K of the present invention 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material involves annealing the discharge plasma sintered body as follows: heating the discharge plasma sintered body to 700-800℃ at a rate of 5℃ / min and holding it at that temperature for 2-4 hours, then cooling it to room temperature at a rate of 5℃ / min.

[0013] According to a second aspect of the present invention, a Ti surface K is provided. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material, the Ti surface K 0.65 Na 0.35 The NbO3 piezoelectric ceramic active coating material was prepared according to the method described above.

[0014] Optionally, the Ti surface K of the present invention 0.65 Na 0.35 The NbO3 piezoelectric ceramic active coating material consists of a Ti substrate and a Ti / K... 0.65 Na 0.35 NbO3 composite gradient connecting layer and K 0.65 Na 0.35 It consists of NbO3 layers.

[0015] According to a third aspect of the invention, it relates to the K surface of Ti. 0.65 Na 0.35 Application of NbO3 piezoelectric ceramic active coating materials as medical materials.

[0016] The Ti surface K of the present invention 0.65 Na 0.35 The NbO3 piezoelectric ceramic active coating material and its preparation method have the following beneficial technical effects:

[0017] 1. Through Ti / K 0.65 Na 0.35 The NbO3 composite gradient bonding layer enables the bonding between the Ti substrate and K... 0.65 Na0.35 The NbO3 layer is stably and firmly bonded.

[0018] 2. By reducing the decomposition of K and Na during low-temperature, rapid sintering through spark plasma sintering, spark plasma sintered bodies with excellent microstructure are prepared. Combined with controllable annealing, Ti surface K exhibits excellent piezoelectric, ferroelectric, dielectric, and bonding properties. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material.

[0019] 3. Through Ti / K 0.65 Na 0.35 By controlling the NbO3 composite powder composition ratio and powder paving parameters, the K content on the Ti surface can be optimized. 0.65 Na 0.35 Precise control of the properties of NbO3 piezoelectric ceramic active coating materials.

[0020] 4. The K-type surface of Ti in this invention 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating materials and their preparation methods can achieve K2 on complex and micro-sized Ti metal surfaces. 0.65 Na 0.35 The preparation of NbO3 piezoelectric ceramic active coating materials has good application prospects. Attached Figure Description

[0021] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 K is from embodiments 1-7 of the present invention. 0.65 Na 0.35 XRD pattern of NbO3 powder; Figure 2 Ti / K prepared in Example 4 of this invention 0.65 Na 0.35 XRD pattern of NbO3 composite powder; Figure 3 K is from embodiments 1-7 of the present invention. 0.65 Na 0.35 SEM image of NbO3 powder; Figure 4 Ti / K prepared in Example 4 of this invention 0.65 Na 0.35 SEM image of NbO3 composite powder; Figure 5The Ti surface K prepared in Examples 1-7 of this invention 0.65 Na 0.35 XRD pattern of NbO3 piezoelectric ceramic active coating material; Figure 6 The Ti surface K prepared according to Examples 2, 3, 4, and 7 of the present invention 0.65 Na 0.35 Cross-sectional SEM image of NbO3 piezoelectric ceramic active coating material; Figure 7 The Ti surface K obtained in Examples 2, 3, 4, and 7 of this invention 0.65 Na 0.35 Cross-sectional scanning image of NbO3 piezoelectric ceramic active coating material; Figure 8 The Ti surface K obtained in Examples 4 and 7 of this invention 0.65 Na 0.35 Cross-sectional line scan of NbO3 piezoelectric ceramic active coating material; Figure 9 The Ti surface K prepared in Examples 1, 2, 4, 6, and 7 of this invention 0.65 Na 0.35 Bar chart of piezoelectric constants of NbO3 piezoelectric ceramic active coating material after polarization; Figure 10 The Ti surface K prepared in Examples 2, 4, and 7 of this invention 0.65 Na 0.35 The surface potential distribution of the NbO3 piezoelectric ceramic active coating material after polarization and the K-value of the Ti surface prepared in Example 4. 0.65 Na 0.35 Surface potential distribution diagram of NbO3 piezoelectric ceramic active coating material before polarization; Figure 11 The Ti surface K prepared in Examples 2, 4, and 7 of this invention 0.65 Na 0.35 The PFM diagrams of the polarized NbO3 piezoelectric ceramic active coating material, from left to right, are the phase diagram, amplitude diagram, and corresponding hysteresis diagram of phase and amplitude. Figure 12 The Ti surface K prepared in Example 4 of this invention 0.65 Na 0.35 Hysteresis loops of NbO3 piezoelectric ceramic active coating material at electric field strengths of 0.5, 1, 2, and 3 kV / mm and a frequency of 10 Hz. Detailed Implementation

[0023] The embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0024] It should be noted that, unless otherwise specified, the following embodiments and features can be combined with each other; and, based on the embodiments of this disclosure, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this disclosure.

[0025] It should be noted that various aspects of embodiments within the scope of the appended claims are described below. It will be apparent that the aspects described herein can be embodied in a wide variety of forms, and any particular structure and / or function described herein is merely illustrative. Based on this disclosure, those skilled in the art will understand that one aspect described herein can be implemented independently of any other aspect, and two or more of these aspects can be combined in various ways. For example, any number of aspects set forth herein can be used to implement the device and / or practice the method. Additionally, this device and / or method can be implemented using structures and / or functionalities other than one or more of the aspects set forth herein. Example 1

[0026] Exemplary Example 1 of the present invention provides a Ti surface K 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material, in this embodiment, the K on the Ti surface 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material is carried out as follows: Step 1: Surface pretreatment of Ti substrate The Ti substrate surface was sprayed with white corundum abrasive with a basic particle size of 100 mesh at a spraying distance of 100 mm for 20 seconds. The Ti substrate was then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 minutes each, and dried at a constant temperature of 40℃.

[0027] Step 2, Ti / K 0.65 Na 0.35 Preparation of NbO3 composite powder With 2g of K 0.65 Na 0.35 Using NbO3 and 8g of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min. 0.65 Na 0.35 NbO3 composite powder.

[0028] Step 3: Powder spreading 0.1g of Ti / K 0.65 Na 0.35NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

[0029] Step 4: Preparation of spark plasma sintered body Ti / K will be laid 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace to obtain the spark plasma sintered body.

[0030] Step 5: Annealing In a muffle furnace, the spark plasma sintered body was heated to 700°C at a rate of 5°C / min and held at that temperature for 3 hours, then cooled to room temperature at a rate of 5°C / min to obtain a Ti surface K 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material. Example 2

[0031] Exemplary Example 2 of the present invention provides a Ti surface K 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material, in this embodiment, the K on the Ti surface 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material is carried out as follows: Step 1: Surface pretreatment of Ti substrate The Ti substrate surface was sprayed with white corundum abrasive with a basic particle size of 100 mesh at a spraying distance of 100 mm for 20 seconds. The Ti substrate was then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 minutes each, and dried at a constant temperature of 40℃.

[0032] Step 2, Ti / K 0.65 Na 0.35 Preparation of NbO3 composite powder With 2g of K 0.65 Na 0.35 Using NbO3 and 8g of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min.0.65 Na 0.35 NbO3 composite powder.

[0033] Step 3: Powder spreading 0.1g of Ti / K 0.65 Na 0.35 NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

[0034] Step 4: Preparation of spark plasma sintered body Ti / K will be laid 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace to obtain the spark plasma sintered body.

[0035] Step 5: Annealing In a muffle furnace, the spark plasma sintered body was heated to 800°C at a rate of 5°C / min and held at that temperature for 3 hours, then cooled to room temperature at a rate of 5°C / min to obtain a Ti surface K 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material. Example 3

[0036] Exemplary Example 3 of the present invention provides a Ti surface K 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material, in this embodiment, the K on the Ti surface 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material is carried out as follows: Step 1: Surface pretreatment of Ti substrate The Ti substrate surface was sprayed with white corundum abrasive with a basic particle size of 100 mesh at a spraying distance of 100 mm for 20 seconds. The Ti substrate was then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 minutes each, and dried at a constant temperature of 40℃.

[0037] Step 2, Ti / K 0.65 Na 0.35Preparation of NbO3 composite powder With 1g of K 0.65 Na 0.35 Using NbO3 and 9g of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min. 0.65 Na 0.35 NbO3 composite powder.

[0038] Step 3: Powder spreading 0.1g of Ti / K 0.65 Na 0.35 NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

[0039] Step 4: Preparation of spark plasma sintered body Ti / K will be laid 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace to obtain the spark plasma sintered body.

[0040] Step 5: Annealing In a muffle furnace, the spark plasma sintered body was heated to 750°C at a rate of 5°C / min and held at that temperature for 3 hours, then cooled to room temperature at a rate of 5°C / min to obtain the K-type surface on the Ti. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material. Example 4

[0041] Exemplary Example 4 of the present invention provides a Ti surface K 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material, in this embodiment, the K on the Ti surface 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material is carried out as follows: Step 1: Surface pretreatment of Ti substrate The Ti substrate surface was sprayed with white corundum abrasive with a basic particle size of 100 mesh at a spraying distance of 100 mm for 20 seconds. The Ti substrate was then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 minutes each, and dried at a constant temperature of 40℃.

[0042] Step 2, Ti / K 0.65 Na 0.35 Preparation of NbO3 composite powder With 2g of K 0.65 Na 0.35 Using NbO3 and 8g of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min. 0.65 Na 0.35 NbO3 composite powder.

[0043] Step 3: Powder spreading 0.1g of Ti / K 0.65 Na 0.35 NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

[0044] Step 4: Preparation of spark plasma sintered body Ti / K will be laid 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace to obtain the spark plasma sintered body.

[0045] Step 5: Annealing In a muffle furnace, the spark plasma sintered body was heated to 750°C at a rate of 5°C / min and held at that temperature for 3 hours, then cooled to room temperature at a rate of 5°C / min to obtain the K-type surface on the Ti. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material. Example 5

[0046] Exemplary Example 5 of the present invention provides a Ti surface K 0.65 Na 0.35The preparation method of NbO3 piezoelectric ceramic active coating material, in this embodiment, the K on the Ti surface 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material is carried out as follows: Step 1: Surface pretreatment of Ti substrate The Ti substrate surface was sprayed with white corundum abrasive with a basic particle size of 100 mesh at a spraying distance of 100 mm for 20 seconds. The Ti substrate was then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 minutes each, and dried at a constant temperature of 40℃.

[0047] Step 2, Ti / K 0.65 Na 0.35 Preparation of NbO3 composite powder With 3g of K 0.65 Na 0.35 Using NbO3 and 7g of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min. 0.65 Na 0.35 NbO3 composite powder.

[0048] Step 3: Powder spreading 0.1g of Ti / K 0.65 Na 0.35 NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

[0049] Step 4: Preparation of spark plasma sintered body Ti / K will be laid 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace to obtain the spark plasma sintered body.

[0050] Step 5: Annealing In a muffle furnace, the spark plasma sintered body was heated to 750°C at a rate of 5°C / min and held at that temperature for 3 hours, then cooled to room temperature at a rate of 5°C / min to obtain the K-type surface on the Ti. 0.65 Na0.35 NbO3 piezoelectric ceramic active coating material. Example 6

[0051] Exemplary Example 6 of the present invention provides a Ti surface K 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material, in this embodiment, the K on the Ti surface 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material is carried out as follows: Step 1: Surface pretreatment of Ti substrate The Ti substrate surface was sprayed with white corundum abrasive with a basic particle size of 100 mesh at a spraying distance of 100 mm for 20 seconds. The Ti substrate was then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 minutes each, and dried at a constant temperature of 40℃.

[0052] Step 2, Ti / K 0.65 Na 0.35 Preparation of NbO3 composite powder With 2g of K 0.65 Na 0.35 Using NbO3 and 8g of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min. 0.65 Na 0.35 NbO3 composite powder.

[0053] Step 3: Powder spreading 0.1g of Ti / K 0.65 Na 0.35 NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

[0054] Step 4: Preparation of spark plasma sintered body Ti / K will be laid 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace to obtain the spark plasma sintered body.

[0055] Step 5: Annealing In a muffle furnace, the spark plasma sintered body was heated to 750°C at a rate of 5°C / min and held at that temperature for 2 hours, then cooled to room temperature at a rate of 5°C / min to obtain K on the Ti surface. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material. Example 7

[0056] Exemplary Example 7 of the present invention provides a Ti surface K 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material, in this embodiment, the K on the Ti surface 0.65 Na 0.35 The preparation method of NbO3 piezoelectric ceramic active coating material is carried out as follows: Step 1: Surface pretreatment of Ti substrate The Ti substrate surface was sprayed with white corundum abrasive with a basic particle size of 100 mesh at a spraying distance of 100 mm for 20 seconds. The Ti substrate was then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 minutes each, and dried at a constant temperature of 40℃.

[0057] Step 2, Ti / K 0.65 Na 0.35 Preparation of NbO3 composite powder With 2g of K 0.65 Na 0.35 Using NbO3 and 8g of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min. 0.65 Na 0.35 NbO3 composite powder.

[0058] Step 3: Powder spreading 0.1g of Ti / K 0.65 Na 0.35 NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

[0059] Step 4: Preparation of spark plasma sintered body Ti / K will be laid 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace to obtain the spark plasma sintered body.

[0060] Step 5: Annealing In a muffle furnace, the spark plasma sintered body was heated to 750°C at a rate of 5°C / min and held at that temperature for 4 hours, then cooled to room temperature at a rate of 5°C / min to obtain a Ti surface K 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material. Example 8

[0061] X-ray powder diffractometer of model SmartLab3KW was used to analyze the K-type particles in Examples 1-7 of this invention. 0.65 Na 0.35 NbO3 powder and Ti / K prepared in Example 4 0.65 Na 0.35 XRD phase analysis was performed on the NbO3 composite powder. Figure 1 K is from embodiments 1-7 of the present invention. 0.65 Na 0.35 XRD pattern of NbO3 powder Figure 2 Ti / K prepared in Example 4 of this invention 0.65 Na 0.35 XRD pattern of NbO3 composite powder.

[0062] like Figure 1 As shown, K 0.65 Na 0.35 NbO3 powder exhibits distinct perovskite diffraction peaks and contains no impurities. For example... Figure 2 As shown, the Ti / K prepared in Example 4 0.65 Na 0.35 NbO3 composite powder possesses K 0.65 Na 0.35 The two phases of NbO3 and TiO2 indicate that after mixing Ti powder, K 0.65 Na 0.35 NbO3 did not undergo a phase transformation, while Ti powder was oxidized to TiO2 phase after ball milling in air.

[0063] The K samples from Examples 1-7 were examined using a scanning electron microscope of model SU8020. 0.65 Na 0.35 NbO3 powder and Ti / K prepared in Example 4 0.65 Na 0.35 Morphology analysis of NbO3 composite powder was performed. Figure 3K is from embodiments 1-7 of the present invention. 0.65 Na 0.35 SEM image of NbO3 powder Figure 4 Ti / K prepared in Example 4 of this invention 0.65 Na 0.35 SEM image of NbO3 composite powder.

[0064] like Figure 3 and Figure 4 As shown, the left figure is K. 0.65 Na 0.35 SEM image of NbO3 powder, right image shows Ti / K 0.65 Na 0.35 SEM image of NbO3 composite gradient bonding layer raw material powder. Ti / K 0.65 Na 0.35 Compared to K, the NbO3 composite gradient bonding layer raw material powder morphology is... 0.65 Na 0.35 The NbO3 powder has no change in morphology and grain size, and its surface is uniformly coated with TiO2 powder, which is beneficial to the bonding of the two phases during subsequent sintering.

[0065] The K-type Ti surfaces prepared in Examples 1-7 were analyzed using a SmartLab3KW X-ray powder diffractometer. 0.65 Na 0.35 XRD phase analysis was performed on the NbO3 piezoelectric ceramic active coating material. Figure 5 The Ti surface K prepared in Examples 1-7 of this invention 0.65 Na 0.35 XRD pattern of NbO3 piezoelectric ceramic active coating material.

[0066] like Figure 5 As shown, the Ti surface K prepared in Examples 1-7 0.65 Na 0.35 XRD diffraction peaks of NbO3 piezoelectric ceramic active coating material and K 0.65 Na 0.35 The NbO3 phase standard card PDF 077-0038 corresponds completely, proving that the Ti surface K prepared in Examples 1-7 is... 0.65 Na 0.35 The NbO3 piezoelectric ceramic active coating material is all K. 0.65 Na 0.35 NbO3 phase, with no other impurities.

[0067] The K-type Ti surfaces prepared in Examples 2, 3, 4, and 7 of this invention were examined using a scanning electron microscope (model SU8020). 0.65 Na 0.35 The cross-section of the NbO3 piezoelectric ceramic active coating material was tested and analyzed. Figure 6The Ti surface K prepared according to Examples 2, 3, 4, and 7 of the present invention 0.65 Na 0.35 Cross-sectional SEM image of NbO3 piezoelectric ceramic active coating material.

[0068] like Figure 6 As shown, the Ti surface K prepared in Examples 2, 3, 4, and 7 of this invention 0.65 Na 0.35 The cross-section of the NbO3 piezoelectric ceramic active coating material consists of three layers, from bottom to top: Ti substrate, Ti / K... 0.65 Na 0.35 NbO3 composite gradient connecting layer and K 0.65 Na 0.35 The NbO3 layer shows a tight bond between the three layers in the cross-section, indicating good bonding and high bonding strength. In Example 4, K... 0.65 Na 0.35 The NbO3 layer thickness is 250 μm, and K in Examples 2, 3, and 7 0.65 Na 0.35 The thickness of the NbO3 layer is 100-200 μm.

[0069] The energy dispersive spectroscopy (EDS) function of a scanning electron microscope (model SU8020) was used to analyze the K content of the Ti surface prepared in Examples 2, 3, 4, and 7 of this invention. 0.65 Na 0.35 The cross-section of the NbO3 piezoelectric ceramic active coating material was tested and analyzed. Figure 7 The Ti surface K obtained in Examples 2, 3, 4, and 7 of this invention 0.65 Na 0.35 Cross-sectional scanning image of NbO3 piezoelectric ceramic active coating material. Figure 8 The Ti surface K obtained in Examples 4 and 7 of this invention 0.65 Na 0.35 Cross-sectional line scan of NbO3 piezoelectric ceramic active coating material.

[0070] Figure 7 The elemental distribution in the cross-section proves that the substrate is Ti from bottom to top, followed by Ti / K. 0.65 Na 0.35 NbO3 composite gradient connecting layer, K 0.65 Na 0.35 The material contains an NbO3 layer and no impurities or component segregation are observed.

[0071] like Figure 8 As shown, the Ti substrate and Ti / K substrate in Examples 4 and 7 0.65 Na 0.35 NbO3 composite gradient connecting layer, K 0.65 Na0.35 In the NbO3 layer, the contents of K, Na, and Nb elements increase layer by layer, while the contents of Ti decrease layer by layer, forming a compositional gradient structure.

[0072] The K-type surfaces of Ti prepared in Examples 1, 2, 4, 6, and 7 of this invention were analyzed using an ET2673D-4 piezoelectric ceramic high-voltage polarizer. 0.65 Na 0.35 The NbO3 piezoelectric ceramic active coating material is polarized, first in K 0.65 Na 0.35 The silver electrode was coated with NbO3, and the polarization conditions were: electric field strength 3kV / mm, polarization temperature 120℃, and polarization time 20min.

[0073] The ZJ-6A model is used. 33 The measuring instrument was used to measure the K content of the Ti surfaces prepared in Examples 1, 2, 4, 6, and 7 after polarization. 0.65 Na 0.35 The piezoelectric constant of NbO3 piezoelectric ceramic active coating material was tested and analyzed. Figure 9 The Ti surface K prepared in Examples 1, 2, 4, 6, and 7 of this invention 0.65 Na 0.35 Bar chart of piezoelectric constants of NbO3 piezoelectric ceramic active coating material after polarization.

[0074] like Figure 9 As shown, the Ti surface K prepared in Examples 1, 2, 4, 6, and 7 0.65 Na 0.35 The piezoelectric constant d of the NbO3 piezoelectric ceramic active coating material 33 The piezoelectric constants are 93±12, 92±13, 102±10, 90±11, and 94±12 pC / N, respectively, in undoped K₂. 0.65 Na 0.35 The level of NbO3 piezoelectric ceramics is relatively high, proving that they all possess good piezoelectric properties.

[0075] The surface potential measurement function of the atomic force microscope (AFM) of Model Dimension Icon was used to measure the K-type surface of the polarized Ti surfaces prepared in Examples 2, 4, and 7. 0.65 Na 0.35 Surface potential of NbO3 piezoelectric ceramic active coating material was tested. Figure 10 The Ti surface K prepared in Examples 2, 4, and 7 of this invention 0.65 Na 0.35 The surface potential distribution of the NbO3 piezoelectric ceramic active coating material after polarization and the K-value of the Ti surface prepared in Example 4. 0.65 Na 0.35 Surface potential distribution of NbO3 piezoelectric ceramic active coating material before polarization.

[0076] like Figure 10 As shown, the Ti surface K prepared in Example 4 0.65 Na 0.35 The surface potentials of the NbO3 piezoelectric ceramic active coating material before and after polarization were 383±65 mV and 532±63 mV, respectively, indicating that polarization can effectively increase the surface potential of the material and help improve its various electrical properties. Examples 2 and 7 show the K-coated Ti surfaces. 0.65 Na 0.35 The surface potentials of the polarized NbO3 piezoelectric ceramic active coating materials are 515±15mV and 521±20mV, respectively, both of which have high surface potentials, similar to those in Example 4.

[0077] The PFM testing function of an atomic force microscope (model Dimension Icon) was used to analyze the K-type Ti surfaces prepared in Examples 2, 4, and 7 after polarization. 0.65 Na 0.35 PFM analysis was performed on the NbO3 piezoelectric ceramic active coating material. Figure 11 The Ti surface K prepared in Examples 2, 4, and 7 of this invention 0.65 Na 0.35 The PFM diagrams of the polarized NbO3 piezoelectric ceramic active coating material, from left to right, are the phase diagram, amplitude diagram, and corresponding hysteresis diagrams of phase and amplitude.

[0078] like Figure 11 As shown, there is a nearly 200° phase difference between the positive and negative phases from -10V to +10V, indicating that the electric field can effectively polarize and switch local polar domains, demonstrating that the K0 on the Ti surface prepared in Examples 2, 4, and 7 is effective. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating materials all possess excellent ferroelectric and piezoelectric properties.

[0079] The K-type ferroelectric analyzer on the Ti surface prepared in Example 4 of this invention was used to analyze the K-type ferroelectric material. 0.65 Na 0.35 Hysteresis loop test was performed on the NbO3 piezoelectric ceramic active coating material. Figure 12 The Ti surface K prepared in Example 4 of this invention 0.65 Na 0.35 Hysteresis loops of NbO3 piezoelectric ceramic active coating material at electric field strengths of 0.5, 1, 2, and 3 kV / mm and a frequency of 10 Hz.

[0080] like Figure 12 As shown in the test results, under the condition that the electric field strength increases, the K on the Ti surface... 0.65 Na 0.35The hysteresis loop of the NbO3 piezoelectric ceramic active coating material becomes fuller and flatter, and the remanent polarization value can reach 32 μC / cm. 2 The coercive field strength is 2.5 kV / mm, which proves that it has good ferroelectric properties.

[0081] In practical applications, the Ti surface K of the embodiments of the present invention 0.65 Na 0.35 The NbO3 piezoelectric ceramic active coating material and its preparation method have the following beneficial technical effects: 1. Through Ti / K 0.65 Na 0.35 The NbO3 composite gradient bonding layer enables the bonding between the Ti substrate and K... 0.65 Na 0.35 The NbO3 layer is stably and firmly bonded.

[0082] 2. By reducing the decomposition of K and Na during low-temperature, rapid sintering through spark plasma sintering, spark plasma sintered bodies with excellent microstructure are prepared. Combined with controllable annealing, Ti surface K exhibits excellent piezoelectric, ferroelectric, dielectric, and bonding properties. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material.

[0083] 3. Through Ti / K 0.65 Na 0.35 By controlling the NbO3 composite powder composition ratio and powder paving parameters, the K content on the Ti surface can be optimized. 0.65 Na 0.35 Precise control of the properties of NbO3 piezoelectric ceramic active coating materials.

[0084] 4. The K-type surface of Ti in this invention 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating materials and their preparation methods can achieve K2 on complex and micro-sized Ti metal surfaces. 0.65 Na 0.35 The preparation of NbO3 piezoelectric ceramic active coating materials has good application prospects.

[0085] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A Ti surface K 0.65 Na 0.35 The method for preparing NbO3 piezoelectric ceramic active coating material is characterized by... The method includes: preparing Ti / K by ball milling. 0.65 Na 0.35 NbO3 composite powder was sequentially layered onto a surface-pretreated Ti matrix using Ti / K composite powder. 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 NbO3 powder was used to prepare a spark plasma sintered body, and the spark plasma sintered body was then annealed to obtain the K on the Ti surface. 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material.

2. The Ti surface K according to claim 1 0.65 Na 0.35 The method for preparing NbO3 piezoelectric ceramic active coating material is characterized by... With 1-3 parts by weight of K 0.65 Na 0.35 Using NbO3 and 7-9 parts by weight of Ti powder as raw materials, Ti / K was obtained by ball milling for 15 minutes at a ball-to-material ratio of 12:1 and a ball milling speed of 300 r / min. 0.65 Na 0.35 NbO3 composite powder.

3. The Ti surface K according to claim 1 0.65 Na 0.35 The method for preparing NbO3 piezoelectric ceramic active coating material is characterized by... The Ti substrate was pretreated by the following method: the Ti substrate surface was sprayed with abrasive, and then ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 min each, and dried at 40℃.

4. The Ti surface K according to claim 3 0.65 Na 0.35 The method for preparing NbO3 piezoelectric ceramic active coating material is characterized by... White corundum abrasive with a basic particle size of 100 mesh was sprayed onto the Ti matrix surface at a spraying distance of 100 mm for 20 seconds.

5. The Ti surface K according to claim 1 0.65 Na 0.35 The method for preparing NbO3 piezoelectric ceramic active coating material is characterized by... 0.1g of Ti / K 0.65 Na 0.35 NbO3 composite powder was laid on a surface-pretreated Ti matrix with a diameter of 10 mm and a height of 1 mm, and 0.15 g of K was added. 0.65 Na 0.35 NbO3 powder is spread on Ti / K 0.65 Na 0.35 On NbO3 composite powder.

6. The Ti surface K according to claim 1 0.65 Na 0.35 The method for preparing NbO3 piezoelectric ceramic active coating material is characterized by... The spark plasma sintered body is prepared as follows: Ti / K-coated materials are laid in a manner that... 0.65 Na 0.35 NbO3 composite powder and K 0.65 Na 0.35 The Ti matrix of NbO3 powder was placed in a spark plasma sintering apparatus, evacuated to 10 Pa, pressurized to 30 MPa, heated to 850 °C at a rate of 100 °C / min and held for 5 min, and then cooled to 350 °C at a rate of 30 °C / min and cooled to room temperature in the furnace.

7. The Ti surface K according to claim 1 0.65 Na 0.35 The method for preparing NbO3 piezoelectric ceramic active coating material is characterized by... Anneal the spark plasma sintered body as follows: heat the spark plasma sintered body to 700-800℃ at a rate of 5℃ / min, hold it at that temperature for 2-4 hours, and then cool it to room temperature at a rate of 5℃ / min.

8. A Ti surface K 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material, characterized in that... The Ti surface K 0.65 Na 0.35 The NbO3 piezoelectric ceramic active coating material is prepared according to the method described in any one of claims 1 to 7.

9. The Ti surface K according to claim 8 0.65 Na 0.35 NbO3 piezoelectric ceramic active coating material, characterized in that... The Ti surface K 0.65 Na 0.35 The NbO3 piezoelectric ceramic active coating material consists of a Ti substrate and a Ti / K composite material. 0.65 Na 0.35 NbO3 composite gradient connecting layer and K 0.65 Na 0.35 It consists of NbO3 layers.

10. The Ti surface K according to any one of claims 8 to 9 0.65 Na 0.35 Application of NbO3 piezoelectric ceramic active coating materials as medical materials.

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