A dual-component reinforced 5y-psz dental ceramic material and a method of making the same

Abstract

The application discloses a kind of based on double-component reinforced 5Y-PSZ dental ceramic materials and preparation method thereof, it is related to ceramic material preparation technical field.The method includes the following steps: ZrCl4 and deionized water are mixed, drop into ammonia solution, and m-ZrO2 Nano ceramic powder is prepared;ZrOCl2·8H2O, Y (NO3) 3·6H2O and deionized water are mixed, m-ZrO2 Nano ceramic powder and polyethylene glycol 2000 are added, and are prepared by calcination, spray granulation, hot-pressing pre-sintering and high-temperature sintering.The application uses nanometer m-phase ZrO2 as reinforcing material, which is dispersedly distributed in 5Y-PSZ, and the volume expansion generated by t-m phase transition of m-phase ZrO2 is used to ensure the anti-aging performance and realize the strengthening of 5Y-PSZ dental ceramic material.The application solves the problem of insufficient strength of 5Y-PSZ dental ceramic material in the prior art.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic material preparation, in particular to a kind of based on dual-component strengthening 5Y-PSZ dental ceramic material and preparation method thereof. BACKGROUND

[0002] Ceramic material, especially Y-TZP ceramic material represented by yttria (Y2O3) stabilized zirconia (ZrO2), has good biocompatibility, excellent mechanical strength and wear resistance, natural and beautiful color and less dental plaque adhesion, which is difficult for resin and metal to achieve, and becomes the current mainstream material of dental ceramic.However, a large number of clinical results show that the traditional high-strength 3Y-TZP (Y2O3 content of 3mol%) dental ceramic material will age in the oral humid environment, resulting in a large number of microcracks in the use process and continuous expansion, which makes the restoration damaged and ineffective, greatly reducing the service life.When the Y2O3 content is increased to 5mol%, the prepared 5Y-PSZ ceramic material hardly ages.However, the increase of Y2O3 content leads to that the strength of the prepared 5Y-PSZ ceramic material is far less than that of 3Y-TZP ceramic, and with the increasing requirements for dental restoration, it is an urgent problem to improve the strength of 5Y-PSZ ceramic.

[0003] At present, the main ways of strengthening 5Y-PSZ ceramic material include fine-grain strengthening and second-phase particle reinforcement, but the strengthening effect is not good, and the material preparation difficulty is greatly increased, which greatly limits the application of the material;In addition, the gradient structure can also be designed, that is, the surface is designed as 5Y-PSZ, and the inside is designed as 3Y-TZP composite structure, which can simultaneously consider the anti-aging performance and mechanical properties of zirconia ceramic material.However, the surface of the gradient structure is still 5Y-PSZ with poor mechanical properties, and the material surface is still easy to be damaged in the long-term use process.Therefore, the existing technical means cannot effectively consider the anti-aging performance and mechanical properties of zirconia-based ceramic. SUMMARY

[0004] In order to solve the above technical problems, the purpose of the present application is to provide a kind of based on dual-component strengthening 5Y-PSZ dental ceramic material and preparation method thereof, to solve the problem of insufficient strength of 5Y-PSZ dental ceramic material in the prior art.

[0005] The technical solution of the present application to solve the above technical problems is as follows: a kind of based on dual-component strengthening 5Y-PSZ dental ceramic material preparation method is provided, comprising the following steps:

[0006] (1) mixing ZrCl4 and deionized water, stirring, dropping in ammonia solution, standing for precipitation, washing, drying, ball milling and sieving, and finally heat treatment, continuing ball milling and sieving, to prepare m-ZrO2 nano ceramic powder;

[0007] (2) mixing ZrOCl2·8H2O, Y(NO3)3·6H2O and deionized water, adding the m-ZrO2 nano ceramic powder prepared in step (1) and polyethylene glycol 2000, to prepare a suspension, stirring, dropping in ammonia solution, standing for precipitation, washing, drying, ball milling and sieving, and finally heat treatment, continuing ball milling and sieving, to prepare m-ZrO2 / 5Y-PSZ nano composite ceramic powder;

[0008] (3) spray granulating the m-ZrO2 / 5Y-PSZ nano composite ceramic powder prepared in step (2) to prepare spherical powder; then hot-pressing pre-sintering to prepare a pre-sintered body; and high-temperature sintering to prepare a dual-component strengthened 5Y-PSZ dental ceramic material.

[0009] Based on the above technical solution, the application can also be improved as follows:

[0010] Further, in step (1), the mass ratio of ZrCl4 to deionized water is (58-94):500.

[0011] Further, in step (1), the mass ratio of ZrCl4 to deionized water is 58:500.

[0012] Further, in step (1), the mass ratio of ZrCl4 to deionized water is 69:500.

[0013] Further, in step (1), the mass ratio of ZrCl4 to deionized water is 94:500.

[0014] Further, in step (1), magnetic stirring is performed.

[0015] Further, the rotating speed of the magnetic stirring is 300-500 r / min.

[0016] Further, in step (1), the concentration of the ammonia solution is 3-5 mol / L.

[0017] Further, in step (1), the concentration of the ammonia solution is 4 mol / L.

[0018] Further, in step (1), the concentration of the ammonia solution is 5 mol / L.

[0019] Further, in step (1), the dropping of the ammonia solution is stopped when the pH value of the system reaches 9.

[0020] Further, in step (1), the standing time is 12 h.

[0021] Further, in step (1), the ball milling time is 24 h.

[0022] Further, in step (1), the mesh size of the sieving is 800 mesh.

[0023] Further, in step (1), the heat treatment is performed under an argon atmosphere and at 600-700℃.

[0024] Further, in step (1), the heat treatment is performed under an argon atmosphere and at 650℃.

[0025] Further, in step (1), the heat treatment is performed under an argon atmosphere and at 700℃.

[0026] Further, in step (2), the mass ratio of ZrOCl2·8H2O, Y(NO3)3·6H2O, deionized water, m-ZrO2 nano ceramic powder and polyethylene glycol 2000 is (76.9-124):(9.6-15.5):500:(3.5-14.2):(10.1-12).

[0027] Further, in step (2), the mass ratio of ZrOCl2·8H2O, Y(NO3)3·6H2O, deionized water, m-ZrO2 nano ceramic powder and polyethylene glycol 2000 is 76.9:9.6:500:3.5:10.1.

[0028] Further, in step (2), the mass ratio of ZrOCl2·8H2O, Y(NO3)3·6H2O, deionized water, m-ZrO2 nano ceramic powder and polyethylene glycol 2000 is 91:11.4:500:7:11.3.

[0029] Further, in step (2), the mass ratio of ZrOCl2·8H2O, Y(NO3)3·6H2O, deionized water, m-ZrO2 nano ceramic powder and polyethylene glycol 2000 is 124:15.5:500:14.2:12.

[0030] Further, in step (2), magnetic stirring is performed.

[0031] Further, the rotation speed of the magnetic stirring is 800-1200 r / min.

[0032] Further, in step (2), the concentration of the ammonia solution is 3-5 mol / L.

[0033] Further, in step (2), the concentration of the ammonia solution is 4 mol / L.

[0034] Further, in step (2), the concentration of the ammonia solution is 5 mol / L.

[0035] Further, in step (2), the ammonia solution is added dropwise until the pH value of the system is 10, and then the dropwise addition is stopped.

[0036] Further, in step (2), the system is allowed to stand for 12 h.

[0037] Further, in step (2), the ball milling time is 24 h.

[0038] Further, in step (2), the mesh number of the sieving is 800.

[0039] Further, in step (2), the heat treatment is performed under an argon atmosphere and at a temperature of 600-700℃.

[0040] Further, in step (2), the heat treatment is performed under an argon atmosphere and at a temperature of 650℃.

[0041] Further, in step (2), the heat treatment is performed under an argon atmosphere and at a temperature of 700℃.

[0042] Further, in step (3), the m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder prepared in step (2) is mixed with deionized water to prepare a mixed solution, polyvinyl alcohol and ammonium polycarboxylate are added, ball milling is performed, drying and sieving are performed to prepare a powder, deionized water is added to prepare a slurry, and then spray granulation is performed to prepare a spherical powder, and the spray granulation process is completed.

[0043] Further, when the powder is prepared, the mass ratio of the m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder to deionized water is 1:3.

[0044] Further, the amount of polyvinyl alcohol added is 1-2 wt% of the mixed solution.

[0045] Further, the amount of polyvinyl alcohol added is 1.5 wt% of the mixed solution.

[0046] Further, the amount of ammonium polycarboxylate added is 0.3-0.6 wt% of the mixed solution.

[0047] Further, the amount of ammonium polycarboxylate added is 0.4 wt% of the mixed solution.

[0048] Further, the sieving is performed through a 150-mesh sieve.

[0049] Further, the content of the powder in the slurry is 0.2 wt%.

[0050] Further, in step (3), the initial pressure is set to 8 MPa, the spherical powder is heated to 600-800°C at a rate of 5°C / min, and at the same time the pressure is increased from 8 MPa to 35 MPa, and then the temperature is kept constant for 2 h, and then the temperature is increased to 900-1100°C at a rate of 3°C / min, and then the temperature is kept constant for 2 h, and then the temperature is cooled and the pressure is reduced to normal pressure, to obtain a pre-sintered body, and the hot-pressing pre-sintering process is completed.

[0051] Further, in step (3), the initial pressure is set to 8 MPa, the spherical powder is heated to 600-800°C at a rate of 5°C / min, and at the same time the pressure is increased from 8 MPa to 35 MPa, and then the temperature is kept constant for 2 h, and then the temperature is increased to 900-1100°C at a rate of 3°C / min, and then the temperature is kept constant for 2 h, and then the temperature is cooled and the pressure is reduced to normal pressure, to obtain a pre-sintered body, and the hot-pressing pre-sintering process is completed.

[0052] Further, in step (3), the initial pressure is set to 8 MPa, the spherical powder is heated to 600-800°C at a rate of 5°C / min, and at the same time the pressure is increased from 8 MPa to 35 MPa, and then the temperature is kept constant for 2 h, and then the temperature is increased to 900-1100°C at a rate of 3°C / min, and then the temperature is kept constant for 2 h, and then the temperature is cooled and the pressure is reduced to normal pressure, to obtain a pre-sintered body, and the hot-pressing pre-sintering process is completed.

[0053] Further, the pressure increasing rate is 0.45 MPa / min, and the pressure decreasing rate is 0.2 MPa / min.

[0054] Further, in step (3), the pre-sintered body is heated from room temperature to 1200°C at a rate of 5°C / min, and then kept constant for 2 h, and then heated from 1200°C to 1400-1500°C at a rate of 3°C / min, and then kept constant for 2-4 h, and then cooled to 1200°C at a rate of 4°C / min, and finally cooled to room temperature, to obtain a 5Y-PSZ dental ceramic material based on dual-component strengthening, and the high-temperature sintering process is completed.

[0055] Further, in step (3), the pre-sintered body is heated from room temperature to 1200°C at a rate of 5°C / min, and then kept constant for 2 h, and then heated from 1200°C to 1450°C at a rate of 3°C / min, and then kept constant for 3 h, and then cooled to 1200°C at a rate of 4°C / min, and finally cooled to room temperature, to obtain a 5Y-PSZ dental ceramic material based on dual-component strengthening, and the high-temperature sintering process is completed.

[0056] Further, in step (3), the pre-sintered body is heated from room temperature to 1200°C at a rate of 5°C / min, and then kept constant for 2 h, and then heated from 1200°C to 1450°C at a rate of 3°C / min, and then kept constant for 3 h, and then cooled to 1200°C at a rate of 4°C / min, and finally cooled to room temperature, to obtain a 5Y-PSZ dental ceramic material based on dual-component strengthening, and the high-temperature sintering process is completed.

[0057] The application also provides the dual-component reinforced 5Y-PSZ dental ceramic material prepared by the method.

[0058] The application also provides application of the dual-component reinforced 5Y-PSZ dental ceramic material in preparation of dental ceramic materials.

[0059] The application has the following beneficial effects:

[0060] 1. For zirconia, there are m phase (at room temperature), t phase (1170 DEG C) and c phase (2300 DEG C), at present, zirconia bulk must be prepared by high-temperature sintering, t-m phase transition (about 1170 DEG C) occurs in the sintering process, causing volume expansion and cracking, and a complete bulk cannot be obtained. The introduction of yttrium oxide can make t phase not change into m phase at room temperature, and realize the preparation of bulk. However, it is not the best to retain all t phase, and a small amount of t-m phase transition is beneficial to the strengthening of zirconia bulk. However, since the dental zirconia ceramic material is applied in the hot and humid environment of the oral cavity, the remaining t phase will gradually change into m phase and cause material damage, that is, aging phenomenon; when the content of yttrium oxide is further increased, the c phase which does not age will be retained in large amounts, the content of t phase will be reduced, the aging performance will be improved, but it also leads to the decrease of t-m phase transition and the significant decrease of strength. Obviously, the dental zirconia material prepared by the traditional single-component raw material cannot meet the requirements of strength and aging resistance. Therefore, the application combines the advantages of t-m strengthening and high c phase content anti-aging, breaks the traditional single-component preparation idea, takes 5Y-PSZ with c phase as the main phase as the matrix, introduces unstable m phase nano zirconia, fully utilizes t-m phase transition to realize effective strengthening, and the main phase of the prepared material is m phase and c phase which do not have aging phenomenon. Compared with the existing fine-grain strengthening and second-phase particle strengthening, the application utilizes the t-m phase transition of nano m phase zirconia in the material preparation process to generate a uniform and dispersed compressive stress field in the 5Y-PSZ ceramic, and the second-phase strengthening also has a good "pinning effect", so that the mechanical properties of the 5Y-PSZ ceramic are improved significantly. In addition, the introduced nano m phase ZrO2 and the main phase c phase in the 5Y-PSZ ceramic matrix are allotropes, and can have good thermal matching with the matrix, effectively avoiding the problem of mismatching of interface thermal expansion coefficient caused by heterogeneous elements. Moreover, the m phase ZrO2 also has certain aesthetic properties and no toxic side effects on human body.

[0061] 2. The application has simple manufacturing process, low raw material cost, and the strengthening effect can be accurately controlled by the amount of m phase ZrO2 introduced, and the application range is wide.

[0062] 3. The biaxial bending strength of the prepared dental ceramic material based on the dual-component reinforced 5Y-PSZ reaches 662 MPa, and the biaxial bending strength of the 5Y-PSZ ceramic material without doping is only 528 MPa, and the biaxial bending strength is increased by 25.4%. BRIEF DESCRIPTION OF DRAWINGS

[0063] Figure 1 The preparation process flow chart of the application is shown in the following figure:

[0064] Figure 2 The XRD pattern of the material prepared in Comparative Example 1 is shown in the following figure:

[0065] Figure 3 The XRD pattern of the dental ceramic material prepared in Example 1 is shown in the following figure:

[0066] Figure 4 The XRD pattern of the dental ceramic material prepared in Example 2 is shown in the following figure:

[0067] Figure 5 The XRD pattern of the dental ceramic material prepared in Example 3 is shown in the following figure:

[0068] Figure 6 The biaxial bending performance test failure diagram of the materials prepared in Examples 1-3 and Comparative Example 1 is shown in the following figure:

[0069] Figure 7 The load-displacement curve diagram of the material prepared in Comparative Example 1 is shown in the following figure:

[0070] Figure 8 The load-displacement curve diagram of the dental ceramic material prepared in Example 1 is shown in the following figure:

[0071] Figure 9 The load-displacement curve diagram of the dental ceramic material prepared in Example 2 is shown in the following figure:

[0072] Figure 10 The load-displacement curve diagram of the dental ceramic material prepared in Example 3 is shown in the following figure. DETAILED DESCRIPTION

[0073] The principles and characteristics of the application are described below in combination with the drawings, and the examples are only used to explain the application and are not used to limit the scope of the application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0074] Polyethylene glycol 2000 is a high molecular polymer with an average molecular weight of about 1900-2200.

[0075] Example 1:

[0076] A kind of based on two-component reinforced 5Y-PSZ dental ceramic material, its preparation method includes the following steps: (preparation process see Figure 1 )

[0077] (1) preparation m-ZrO2 Nano ceramic powder

[0078] ZrCl4 and deionized water are mixed, the prepared solution is magnetically stirred, the rotating speed of magnetic stirring is 300r / min, while dropping into ammonia solution (concentration is 3mol / L), until the pH value of system is 9, stop dropping, deposit for 12h, then wash, dry, ball mill for 24h and pass 800 mesh screen, obtain precipitate, finally heat treatment under argon atmosphere and 600 DEG C condition, continue ball milling for 24h and pass 800 mesh screen, prepare m-ZrO2 Nano ceramic powder;Wherein, the mass ratio of ZrCl4 and deionized water is 58:500;

[0079] (2) preparation m-ZrO2 / 5Y-PSZ nano composite ceramic powder

[0080] ZrOCl2·8H2O, Y (NO3) 3·6H2O and deionized water are mixed, the m-ZrO2 Nano ceramic powder prepared in step (1) and polyethylene glycol 2000 are added, a suspension is prepared, the suspension is magnetically stirred, the rotating speed of magnetic stirring is 800r / min, while dropping into ammonia solution (concentration is 3mol / L), until the pH value of system is 10, stop dropping, deposit, then wash, dry, ball mill for 24h and pass 800 mesh screen, finally heat treatment under argon atmosphere and 600 DEG C condition, continue ball milling for 24h and pass 800 mesh screen, prepare m-ZrO2 / 5Y-PSZ nano composite ceramic powder;Wherein, the mass ratio of ZrOCl2·8H2O, Y (NO3) 3·6H2O, deionized water, m-ZrO2 Nano ceramic powder and polyethylene glycol 2000 is 76.9:9.6:500:3.5:10.1;

[0081] (3) spray granulation

[0082] The m-ZrO2 / 5Y-PSZ nano composite ceramic powder prepared in step (2) and deionized water are mixed uniformly to prepare a mixed solution, polyvinyl alcohol and ammonium polycarboxylate are added, ball milling, drying, passing 150 mesh screen, to prepare a powder, adding deionized water to prepare a slurry (the content of powder in the slurry is 0.2wt%), then spray granulation, to prepare spherical powder, complete the spray granulation process;Wherein, when preparing the powder, the mass ratio of m-ZrO2 / 5Y-PSZ nano composite ceramic powder and deionized water is 1:3, the addition amount of polyvinyl alcohol is 1wt% of the mixed solution, and the addition amount of ammonium polycarboxylate is 0.3wt% of the mixed solution;

[0083] (4) Hot-pressing pre-sintering

[0084] The spherical powder prepared in step (3) is placed in a hot-pressing furnace, an initial pressure of 8 MPa is set, and the temperature is raised to 600℃ at a rate of 5℃ / min, during which the pressure is gradually increased from 8 MPa to 35 MPa, and the temperature is kept constant for 2h, then the temperature is raised to 900℃ at a rate of 3℃ / min, and the temperature is kept constant for 2h, and then cooled and depressurized to normal pressure, to obtain a pre-sintered body, and the hot-pressing pre-sintering process is completed; wherein the pressure increasing rate is 0.45 MPa / min, and the pressure decreasing rate is 0.2 MPa / min;

[0085] (5) High-temperature sintering

[0086] The pre-sintered body prepared in step (4) is placed in a heat treatment furnace, and the temperature is raised from room temperature to 1200℃ at a rate of 5℃ / min, and the temperature is kept constant for 2h, then the temperature is raised from 1200℃ to 1400℃ at a rate of 3℃ / min, and the temperature is kept constant for 4h, then the temperature is lowered to 1200℃ at a rate of 4℃ / min, and finally cooled to room temperature, to obtain a dual-component reinforced 5Y-PSZ dental ceramic material, and the high-temperature sintering process is completed.

[0087] Example 2:

[0088] A dual-component reinforced 5Y-PSZ dental ceramic material, the preparation method comprising the following steps:

[0089] (1) Preparation of m-ZrO2 nano ceramic powder

[0090] ZrCl4 and deionized water are mixed, the prepared solution is subjected to magnetic stirring, the rotation speed of the magnetic stirring is 400r / min, and an ammonia solution (concentration of 4mol / L) is dropped into the system at the same time, until the pH value of the system is 9, the dropping is stopped, and the system is left to stand for 12h for precipitation, then washed, dried, ball milled for 24h and sieved through an 800 mesh sieve, to obtain a precipitate, and finally subjected to heat treatment under an argon atmosphere at 650℃, and then ball milled for 24h and sieved through an 800 mesh sieve, to obtain the m-ZrO2 nano ceramic powder; wherein the mass ratio of ZrCl4 to deionized water is 69:500;

[0091] (2) Preparation of m-ZrO2 / 5Y-PSZ nano composite ceramic powder

[0092] ZrOCl2·8H2O, Y(NO3)3·6H2O and deionized water were mixed, and the m-ZrO2 nano-ceramic powder obtained in step (1) and polyethylene glycol 2000 were added to prepare a suspension. The suspension was magnetically stirred at a speed of 1000 r / min, and ammonia solution (concentration of 4 mol / L) was added dropwise until the pH of the system reached 10. The addition was then stopped, and the mixture was allowed to stand for precipitation. The mixture was then washed, dried, and... The powder was ball-milled for 24 hours and passed through an 800-mesh sieve. Finally, it was heat-treated under an argon atmosphere at 650℃, followed by ball milling for another 24 hours and passing through an 800-mesh sieve to obtain m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder. The mass ratio of ZrOCl2·8H2O, Y(NO3)3·6H2O, deionized water, m-ZrO2 nanocomposite ceramic powder, and polyethylene glycol 2000 was 91:11.4:500:7:11.3.

[0093] (3) Spray granulation

[0094] The m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder obtained in step (2) was mixed evenly with deionized water to obtain a mixed solution. Polyvinyl alcohol and ammonium polycarboxylate were added, and the mixture was ball-milled, dried, and passed through a 150-mesh sieve to obtain powder. Deionized water was added to obtain a slurry (the content of powder in the slurry was 0.2wt%). Then, the mixture was spray-granulated to obtain spherical powder, thus completing the spray-granulation process. When the powder was obtained, the mass ratio of m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder to deionized water was 1:3, the amount of polyvinyl alcohol added was 1.5wt% of the mixed solution, and the amount of ammonium polycarboxylate added was 0.4wt% of the mixed solution.

[0095] (4) Hot pressing and pre-sintering

[0096] The spherical powder obtained in step (3) is placed in a hot press furnace, the initial pressure is set to 8 MPa, and the temperature is increased to 700℃ at a rate of 5℃ / min. During this process, the pressure is gradually increased from 8 MPa to 35 MPa, and the temperature and pressure are maintained for 2 hours. Then the temperature is increased to 1000℃ at a rate of 3℃ / min, and the temperature is maintained for 2 hours. Then the temperature is cooled and the pressure is reduced to normal pressure to obtain a pre-sintered body and complete the hot pressing pre-sintering process. The pressure increase rate is 0.45 MPa / min and the pressure decrease rate is 0.2 MPa / min.

[0097] (5) High-temperature sintering

[0098] The pre-sintered body prepared in step (4) is placed in a heat treatment furnace, heated from room temperature to 1200°C at a rate of 5°C / min, kept for 2h, then heated from 1200°C to 1450°C at a rate of 3°C / min, kept for 3h, then cooled to 1200°C at a rate of 4°C / min, and finally cooled to room temperature, to prepare a dual-component reinforced 5Y-PSZ dental ceramic material, and complete the high-temperature sintering process.

[0099] Example 3:

[0100] A dual-component reinforced 5Y-PSZ dental ceramic material, the preparation method comprising the following steps:

[0101] (1) Preparation of m-ZrO2 nano ceramic powder

[0102] ZrCl4 and deionized water are mixed, the prepared solution is subjected to magnetic stirring at a speed of 500r / min, an ammonia solution (concentration of 5mol / L) is dropped into the system, until the pH value of the system is 9, the dropping is stopped, and the system is left to stand for 12h for precipitation, then washed, dried, ball-milled for 24h, and passed through an 800-mesh sieve, to obtain a precipitate, which is finally subjected to heat treatment under an argon atmosphere at 700°C, and then ball-milled for 24h and passed through an 800-mesh sieve, to prepare the m-ZrO2 nano ceramic powder; wherein the mass ratio of ZrCl4 to deionized water is 94:500.

[0103] (2) Preparation of m-ZrO2 / 5Y-PSZ nano composite ceramic powder

[0104] ZrOCl2·8H2O, Y(NO3)3·6H2O and deionized water are mixed, the m-ZrO2 nano ceramic powder prepared in step (1) and polyethylene glycol 2000 are added, to prepare a suspension, the suspension is subjected to magnetic stirring at a speed of 1200r / min, an ammonia solution (concentration of 5mol / L) is dropped into the system, until the pH value of the system is 10, the dropping is stopped, and the system is left to stand for precipitation, then washed, dried, ball-milled for 24h, and passed through an 800-mesh sieve, and finally subjected to heat treatment under an argon atmosphere at 700°C, and then ball-milled for 24h and passed through an 800-mesh sieve, to prepare the m-ZrO2 / 5Y-PSZ nano composite ceramic powder; wherein the mass ratio of ZrOCl2·8H2O, Y(NO3)3·6H2O, deionized water, m-ZrO2 nano ceramic powder and polyethylene glycol 2000 is 124:15.5:500:14.2:12.

[0105] (3) Spray granulation

[0106] The m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder prepared in step (2) and deionized water are mixed uniformly to prepare a mixed solution, polyvinyl alcohol and ammonium polycarboxylate are added, ball milling is performed, drying is performed, the powder is passed through a 150-mesh sieve, deionized water is added to prepare a slurry (the content of the powder in the slurry is 0.2 wt%), and then spray granulation is performed to prepare spherical powder, and the spray granulation process is completed; wherein, when the powder is prepared, the mass ratio of the m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder to deionized water is 1:3, the addition amount of polyvinyl alcohol is 2 wt% of the mixed solution, and the addition amount of ammonium polycarboxylate is 0.6 wt% of the mixed solution.

[0107] (4) Hot-pressing pre-sintering

[0108] The spherical powder prepared in step (3) is placed in a hot-pressing furnace, the initial pressure is set to 8 MPa, the temperature is raised to 800℃ at a rate of 5℃ / min, the pressure is gradually increased from 8 MPa to 35 MPa during this process, the temperature is kept constant and the pressure is kept constant for 2 h, then the temperature is raised to 1100℃ at a rate of 3℃ / min, the temperature is kept constant for 2 h, and then the temperature is cooled and the pressure is reduced to atmospheric pressure to prepare a pre-sintered body, and the hot-pressing pre-sintering process is completed; wherein, the pressure increasing rate is 0.45 MPa / min, and the pressure decreasing rate is 0.2 MPa / min.

[0109] (5) High-temperature sintering

[0110] The pre-sintered body prepared in step (4) is placed in a heat treatment furnace, the temperature is raised from room temperature to 1200℃ at a rate of 5℃ / min, the temperature is kept constant for 2 h, then the temperature is raised from 1200℃ to 1500℃ at a rate of 3℃ / min, the temperature is kept constant for 2 h, then the temperature is reduced to 1200℃ at a rate of 4℃ / min, and finally the temperature is cooled to room temperature to prepare a dual-component reinforced 5Y-PSZ dental ceramic material, and the high-temperature sintering process is completed.

[0111] Comparative Example 1:

[0112] A 5Y-PSZ material of an undoped m-ZrO2 nanoceramic powder, the preparation method comprising the following steps:

[0113] Without step (1), the rest is the same as Example 1.

[0114] Comparative Example 2:

[0115] A 5Y-PSZ material of an undoped m-ZrO2 nanoceramic powder, the preparation method comprising the following steps:

[0116] Without step (1), the rest is the same as Example 2.

[0117] Comparative Example 3:

[0118] A 5Y-PSZ material of an undoped m-ZrO2 nanoceramic powder, a preparation method thereof comprises the following steps:

[0119] Without step (1), the rest is the same as example 3.

[0120] Test example:

[0121] I. XRD object analysis

[0122] The 5Y-PSZ dental ceramic materials based on dual-component reinforcement prepared by examples 1-3 and the materials prepared by comparative examples were respectively subjected to XRD spectrum test, wherein the products prepared by comparative examples 1-3 are basically the same, and the following takes comparative example 1 as a representative of comparative examples, and the results are shown in Figures 2-5 .

[0123] It can be seen from Figures 2-5 that after being doped with m-ZrO2, the m phase in the products prepared by examples 1-3 is significantly increased, and the m phase in the comparative example 1 without doping m-ZrO2 is extremely low, which indicates that a large amount of t-m phase change is generated in the preparation process of the 5Y-PSZ after doping m-ZrO2.

[0124] II. Biaxial bending test

[0125] The 5Y-PSZ dental ceramic materials based on dual-component reinforcement prepared by examples 1-3 and the materials prepared by comparative examples were respectively subjected to biaxial bending test, wherein the products prepared by comparative examples 1-3 are basically the same, and the following takes comparative example 1 as a representative of comparative examples;

[0126] The detection method is specifically:

[0127] According to the biaxial bending strength test standard in the international standard ISO 6872:2024 of dental ceramic materials, a universal testing machine is used for biaxial bending strength test, the sample size is 15 (± 0.5) mm x 1.5 (± 0.2) mm, the loading range is 2kN, the loading speed is 0.5mm / min, the inlet force is set to 5N, the computer collects related data through the load and displacement sensors, and the biaxial bending strength is obtained through the following calculation formula:

[0128]

[0129] Among them:

[0130]

[0131] In the formula: σ is the biaxial bending strength, MPa; P is the maximum load, N; b is the thickness of the sample, mm; υ is the Poisson's ratio of the material, taking 0.25; r1 is the support circle radius, mm; r2 is the load area radius, mm; r3 is the sample radius, mm.

[0132] The biaxial bending performance test procedure is as follows: Figure 6 ( Figure 6 In the image, (a) shows the test mold and the sample of Example 1 before testing; (b) shows the actual image of the fractured sample of Comparative Example 1 after testing; (c) shows the actual image of the fractured sample of Example 1 after testing; (d) shows the actual image of the fractured sample of Example 2 after testing; and (e) shows the actual image of the fractured sample of Example 3 after testing.

[0133] Load-displacement correlation data during biaxial bending testing can be found in [reference needed]. Figures 7-10 The results of biaxial bending strength are shown in Table 1.

[0134] Table 1 Results of Biaxial Bending Strength Test

[0135]

[0136] Depend on Figures 7-10 It can be seen that the addition of m-ZrO2 in this invention did not change the fracture characteristics of the 5Y-PSZ material, which still exhibited typical brittle fracture characteristics.

[0137] As shown in Table 1, the biaxial bending strength of the 5Y-PSZ dental ceramic material prepared by the process of this invention is greater than 500 MPa, meeting the strength requirements for ceramic teeth (greater than 100 MPa for anterior teeth and greater than 500 MPa for molars) in the international standard ISO 6872:2024 for dental ceramic materials. In Example 2, the sample after biaxial bending strengthening achieved a maximum biaxial bending strength of 662 MPa, while the unstrengthened 5Y-PSZ ceramic material in Comparative Example 2 only achieved a biaxial bending strength of 528 MPa. The biaxial bending strength of this invention is increased by 25.4%, demonstrating a significant strengthening effect.

[0138] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing dental ceramic material based on dual-component reinforced 5Y-PSZ, characterized in that, Includes the following steps: (1) Mix ZrCl4 and deionized water, stir, and add ammonia solution dropwise. Let stand to precipitate, then wash, dry, ball mill and sieve, and finally heat treat. Continue ball milling and sieve to obtain m-ZrO2 nano-ceramic powder. (2) Mix ZrOCl2·8H2O, Y(NO3)3·6H2O and deionized water, add the m-ZrO2 nano-ceramic powder obtained in step (1) and polyethylene glycol 2000 to obtain a suspension, stir, add ammonia solution dropwise, let stand to precipitate, then wash, dry, ball mill and sieve, finally heat treat, continue ball milling and sieve to obtain m-ZrO2 / 5Y-PSZ nano-composite ceramic powder; (3) Spray granulation was performed on the m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder obtained in step (2) to obtain spherical powder; then hot pressing and pre-sintering were performed to obtain a pre-sintered body; then high-temperature sintering was performed to obtain dental ceramic material based on dual-component reinforced 5Y-PSZ. In step (2), the mass ratio of ZrOCl2·8H2O, Y(NO3)3·6H2O, deionized water, m-ZrO2 nano-ceramic powder and polyethylene glycol 2000 is (76.9-124): (9.6-15.5): 500: (3.5-14.2): (10.1-12).

2. The preparation method of dental ceramic material based on dual-component reinforced 5Y-PSZ according to claim 1, characterized in that, In step (1), the mass ratio of ZrCl4 to deionized water is (58-94):

500.

3. The preparation method of dental ceramic material based on dual-component reinforced 5Y-PSZ according to claim 1, characterized in that, In step (1), ammonia solution is added dropwise until the pH of the system is 9, at which point the addition is stopped.

4. The preparation method of dental ceramic material based on dual-component reinforced 5Y-PSZ according to claim 1, characterized in that, In step (1), heat treatment is carried out in an argon atmosphere at 600-700℃.

5. The preparation method of dental ceramic material based on dual-component reinforced 5Y-PSZ according to claim 1, characterized in that, In step (2), heat treatment is carried out in an argon atmosphere at 600-700℃.

6. The preparation method of dental ceramic material based on dual-component reinforced 5Y-PSZ according to claim 1, characterized in that, In step (3), the m-ZrO2 / 5Y-PSZ nanocomposite ceramic powder obtained in step (2) is mixed evenly with deionized water to obtain a mixed solution. Polyvinyl alcohol and ammonium polycarboxylate are added, and the mixture is ball-milled, dried, and sieved to obtain powder. Deionized water is added to obtain a slurry, and then spray granulation is performed to obtain spherical powder, thus completing the spray granulation process.

7. The preparation method of dental ceramic material based on dual-component reinforced 5Y-PSZ according to claim 1, characterized in that, In step (3), the initial pressure is set to 8 MPa, the spherical powder is heated to 600-800℃ at a rate of 5℃ / min, and the pressure is increased from 8 MPa to 35 MPa at the same time. The temperature and pressure are maintained for 2 hours, and then the temperature is increased to 900-1100℃ at a rate of 3℃ / min. The temperature is maintained for 2 hours, and then the powder is cooled and the pressure is reduced to normal pressure to obtain a pre-sintered body, thus completing the hot pressing pre-sintering process.

8. The preparation method of dental ceramic material based on dual-component reinforced 5Y-PSZ according to claim 1, characterized in that, In step (3), the pre-sintered body is heated from room temperature to 1200℃ at a rate of 5℃ / min and held for 2 hours. Then, it is heated from 1200℃ to 1400-1500℃ at a rate of 3℃ / min and held for 2-4 hours. Then, it is cooled to 1200℃ at a rate of 4℃ / min and finally cooled to room temperature to obtain the dental ceramic material based on the dual-component reinforced 5Y-PSZ, thus completing the high-temperature sintering process.

9. A dental ceramic material based on dual-component reinforced 5Y-PSZ, characterized in that, It was prepared using the preparation method of the dual-component reinforced 5Y-PSZ dental ceramic material as described in any one of claims 1-8.

Images