CN113800907B - Dental zirconia ceramic slurry for 3D printing and preparation method and application thereof - Google Patents
Dental zirconia ceramic slurry for 3D printing and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to dental zirconia ceramic slurry for 3D printing and a preparation method and application thereof, wherein the fluid property of the zirconia ceramic slurry and the mechanical property of a printing blank are further improved through the grain composition of zirconia powder with different grain diameters.
Description
Technical Field
The invention belongs to the technical field of printing materials for additive manufacturing, relates to dental zirconia ceramic slurry for 3D printing, and particularly relates to dental zirconia ceramic slurry for 3D printing, a preparation method and application thereof.
Background
The zirconia biological ceramics have good biocompatibility and mechanical properties, and are widely applied to the preparation of artificial teeth, artificial joints, artificial bones and other human implants. However, the traditional ceramic preparation technology has the problems of long production period, high manufacturing cost, difficulty in manufacturing ceramic samples with complex shapes and the like, so that the application and development of the zirconia biological ceramic in the medical field are restricted.
In recent years, 3D printing ceramic technology based on extrusion molding is an important ceramic material additive manufacturing process, and has attracted more and more attention and research due to advantages of simple process flow, low equipment cost, wider material applicability, and the like.
The key of the ceramic material 3D printing technology based on extrusion forming is to prepare ceramic slurry with high solid content, good flow characteristic and printability. In the prior art, solid content and fluidity are a pair of contradictions which are difficult to solve, solid content is improved, free liquid in the slurry is reduced, so that poor fluidity of the slurry is caused, the printability is influenced, and the phenomena of blockage, agglomeration and the like are easily caused in the printing process. On the contrary, if more solvent is added in the process of preparing the slurry, the ceramic powder particles can be fully wetted, the fluidity of the slurry is increased, the printability is improved, but the solid content of the ceramic powder particles in a ceramic slurry suspension system is low, the shrinkage rate of a printed ceramic blank body is improved after high-temperature sintering, the compactness is reduced, deformation, cracks and other phenomena can be caused, and the mechanical performance of the sintered ceramic blank body is further influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide dental zirconia ceramic slurry for 3D printing, a preparation method and application thereof.
The technical problem to be solved by the invention is realized by the following technical scheme:
a dental zirconia ceramic slurry for 3D printing, characterized by: comprises solid raw materials, a dispersant, a binder, a plasticizer, a lubricant and a pH regulator;
the solid raw materials comprise the following components in percentage by mass:
290-100% of submicron zirconia ZrO
20-10% of nano-grade zirconium oxide ZrO;
the dispersing agent is sodium polyacrylate;
the adhesive is hydantoin epoxy resin;
the plasticizer is polyethylene glycol;
the lubricant is glycerol;
the pH regulator is sodium hydroxide.
A preparation method of dental zirconia ceramic slurry for 3D printing is characterized by comprising the following steps: the method comprises the following steps:
1) Grading zirconia: grading the two zirconia powders with different particle sizes according to different mass ratios;
2) Preparing a premixed solution: sequentially adding a dispersant sodium polyacrylate, a binder with the hydantoin epoxy resin content of 3wt%, a plasticizer with the polyethylene glycol content of 0.2wt% and a lubricant with the glycerol content of 0.3wt% into deionized water to prepare a premixed solution of the double-particle-size zirconia ceramic slurry, magnetically stirring the premixed solution at the speed of 60rpm for 20 minutes until the solution is completely dissolved, and dripping a sodium hydroxide solution into the premixed solution to adjust the pH value to 10.8-11.0;
3) Mixing materials: putting the two weighed zirconia powder bodies into a ball-milling tank in sequence according to a grading relationship, adding the premixed solution obtained in the step 2), carrying out ball-milling mixing to prepare dual-particle-size zirconia ceramic slurry with the solid content of 58vol.%, using zirconia balls with the diameter of 10mm as a ball-milling medium, wherein the ball-milling ratio is 1.
Use of dental zirconia ceramic slurry for 3D printing, characterized in that: the method comprises the following steps:
1) The method comprises the following steps of (1) loading uniformly mixed zirconia ceramic slurry with different grading relations into a charging barrel, pushing a plunger to extrude the material by using an air pump, and adjusting extrusion air pressure according to rheological properties of different ceramic slurries so that the diameter of an extruded filament is about 1.2 times of the diameter of a printing needle head, the extruded filament is not stretched or wound under the condition that the printing speed is 12mm/s, the diameter of the printing needle head is selected to be 0.5mm, and the thickness of the layer is 1.2 times of the diameter of the printing needle head;
2) Drying the printed ceramic sample piece for 24 hours at room temperature, then placing the ceramic sample piece into a box furnace for degreasing and sintering, firstly heating the dried ceramic sample piece to 600 ℃ at the heating rate of 2 ℃/min for degreasing, degreasing for 1 hour, then heating to 1550 ℃ at the heating rate of 3 ℃/min for sintering, after sintering for 2 hours, cooling to 500 ℃ at the cooling rate of 3 ℃/min, finally cooling to room temperature along with the furnace, manually polishing and polishing the sintered blank body for use, and printing the prepared ceramic slurry into a tooth blank by an extrusion process, wherein a 3D printer is a 3D printing platform provided with a micro-flow extrusion molding head device.
The invention has the advantages and beneficial effects that:
according to the invention, the particle grading is carried out on the ceramic particles by using a particle accumulation theory, so that the pores among the ceramic particles are reduced, the solid content of the ceramic slurry is improved, the rheological property of the zirconia ceramic slurry is improved, and the compactness, the bending strength and the fracture toughness of the sintered ceramic are increased.
Drawings
FIG. 1 is a flow chart of a process for preparing a zirconia slurry according to the present invention;
FIG. 2 is a graph of rheological properties of various grain-graded zirconia ceramic slurries of the present invention;
FIG. 3 is a graph of linear shrinkage and relative density of sintered zirconia ceramics of different grain sizes according to the present invention;
FIG. 4 is a graph showing the bending strength of zirconia ceramics with different grain composition according to the present invention;
FIG. 5 is a graph of fracture toughness for different grain-graded zirconia of the present invention;
FIG. 6 is a micro-topography of the cross-section of the green body under different grain composition conditions of examples 1-6, wherein (a) is the micro-topography of the cross-section of example 1; (b) is the cross-sectional micro-topography of example 2; (c) the microstructure of the cross section of example 3; (d) the cross-sectional microtopography of example 4; (e) the microstructure of the cross section of example 5; and (f) is the cross-sectional micro-topography of example 6.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
A dental zirconia ceramic slurry for 3D printing, characterized by: comprises solid raw materials, a dispersant, a binder, a plasticizer, a lubricant and a pH regulator;
the solid raw materials comprise the following components in percentage by mass:
290-100% of submicron zirconia ZrO
20-10% of nano-grade zirconium oxide ZrO;
the dispersing agent is sodium polyacrylate;
the adhesive is hydantoin epoxy resin;
the plasticizer is polyethylene glycol;
the lubricant is glycerol;
the pH regulator is sodium hydroxide.
A preparation method of dental zirconia ceramic slurry for 3D printing is characterized by comprising the following steps: the method comprises the following steps:
1) 1) zirconia grading: grading two kinds of zirconia powder with different particle sizes according to different mass ratios, wherein the different particle grades and the content of a dispersing agent are shown in table 1;
TABLE 1 particle composition and dispersant content
2) Preparing a premixed solution: sequentially adding a dispersant sodium polyacrylate, a binder with the hydantoin epoxy resin content of 3wt%, a plasticizer with the polyethylene glycol content of 0.2wt% and a lubricant with the glycerol content of 0.3wt% into deionized water to prepare a premixed solution of the double-particle-size zirconia ceramic slurry, magnetically stirring the premixed solution at the speed of 60rpm for 20 minutes until the solution is completely dissolved, and dripping a sodium hydroxide solution into the premixed solution to adjust the pH value to 10.8-11.0;
3) Mixing materials: putting the two weighed zirconia powder bodies into a ball-milling tank in sequence according to a grading relationship, adding the premixed solution obtained in the step 2), carrying out ball-milling mixing to prepare dual-particle-size zirconia ceramic slurry with the solid content of 58vol.%, using zirconia balls with the diameter of 10mm as a ball-milling medium, wherein the ball-milling ratio is 1.
Use of dental zirconia ceramic slurry for 3D printing, characterized in that: the method comprises the following steps:
1) The uniformly mixed zirconia ceramic slurry with different grading relations is filled into a charging barrel, a plunger is pushed by an air pump to extrude the material, the extruding air pressure is adjusted according to the rheological characteristics of different ceramic slurries, so that the diameter of an extruded filament is about 1.2 times of the diameter of a printing needle head, the extruded filament is not stretched or wound under the condition that the printing speed is 12mm/s, the diameter of the printing needle head is selected to be 0.5mm, and the thickness of the layer is 1.2 times of the diameter of the printing needle head;
2) Drying the printed ceramic sample piece for 24 hours at room temperature, then placing the ceramic sample piece into a box furnace for degreasing and sintering, firstly heating the dried ceramic sample piece to 600 ℃ at the heating rate of 2 ℃/min for degreasing, degreasing for 1 hour, then heating to 1550 ℃ at the heating rate of 3 ℃/min for sintering, after sintering for 2 hours, cooling to 500 ℃ at the cooling rate of 3 ℃/min, finally cooling to room temperature along with the furnace, manually polishing and polishing the sintered blank body for use, and printing the prepared ceramic slurry into a tooth blank by an extrusion process, wherein a 3D printer is a 3D printing platform provided with a micro-flow extrusion molding head device.
Example 1
90g of submicron and 10g of nano-zirconia powder are graded, and a dispersant sodium polyacrylate, a binder hydantoin epoxy resin, a plasticizer polyethylene glycol and a lubricant glycerol are sequentially added into deionized water to prepare a premixed solution of the double-particle-size zirconia ceramic slurry. The premix solution was magnetically stirred at 60rpm for 20 minutes to completely dissolve the organic additives. And dripping sodium hydroxide solution into the premixed solution to adjust the pH value to 10.8-11. The components of the ceramic powder are shown in table 2:
TABLE 2 ingredient Table of ceramic powder
| Ceramic powder | Submicron zirconia | Nanoscale zirconia |
| Mass fraction (percentage) | 90 | 10 |
The components of the zirconia ceramic slurry are shown in table 3:
TABLE 3 composition of zirconia ceramic slurries
And sequentially putting the two weighed zirconia powder bodies into a 50ml ball-milling tank according to the grading relation, adding corresponding premixed solution, and carrying out ball-milling mixing to prepare the dual-particle-size zirconia ceramic slurry with the solid content of 58 vol.%. In the ball milling process, zirconia balls with the diameter of 10mm are used as ball milling media, the ball material ratio is 1.
And (3) filling the prepared ceramic slurry into a charging barrel, defoaming, and extruding and forming the slurry by using a micro-flow extrusion ceramic 3D printer. The extrusion air pressure was adjusted according to the rheological properties of the different ceramic pastes so that the diameter of the extruded filaments was about 1.2 times the diameter of the print head outlet and no stretching or twisting occurred at a print speed of 12 mm/s. The diameter of the outlet of the printing nozzle is 0.5mm, and the thickness of the layer of the 3D printer is 1.2 times of the diameter of the outlet of the nozzle. The specific printing process parameters are shown in table 4:
table 4 3d print platform process parameters
And drying the printed ceramic sample piece for 24 hours at room temperature, and then putting the ceramic sample piece into a box furnace for degreasing and sintering. The dried ceramic sample piece is firstly heated to 600 ℃ at the heating rate of 2 ℃/min for degreasing, then heated to 1550 ℃ at the heating rate of 3 ℃/min for sintering after degreasing for 1h, and finally cooled to the room temperature along with the furnace at the cooling rate of 3 ℃/min after sintering for 2h, and the sintered blank is manually polished and polished.
Example 2
In the method for preparing zirconia ceramic slurry for 3D printing in this example, the components of the ceramic powder and the mass fractions of the components are shown in table 5, and the components of the ceramic slurry and the mass fractions of the components are shown in table 6.
Table 5 composition table of ceramic powder (mass fraction%)
| Ceramic powder | Submicron zirconia | Nanoscale zirconia |
| Mass fraction (%) | 93 | 7 |
Table 6 composition of zirconia ceramic slurry (mass fraction,%)
The other steps were the same as in example 1, and the product obtained was the same as in example 1.
Example 3
In the method for preparing zirconia ceramic slurry for 3D printing in this example, the components of the ceramic powder and the mass fractions of the components are shown in table 7, and the components of the ceramic slurry and the mass fractions of the components are shown in table 8.
TABLE 7 ingredient Table of ceramic powder (mass fraction%)
| Ceramic powder | Submicron zirconia | Nanoscale zirconia |
| Mass fraction (%) | 95 | 5 |
TABLE 8 ingredients of zirconia ceramic slurry (mass fraction%)
The other steps were the same as in example 1, and the product obtained was the same as in example 1.
Example 4
In the preparation method of zirconia ceramic slurry for 3D printing in this example, the components of the ceramic powder and the mass fractions of the components are shown in table 9, and the components of the ceramic slurry and the mass fractions of the components are shown in table 10.
TABLE 9 composition of ceramic powder (mass fraction%)
| Ceramic powder | Submicron zirconia | Nanoscale zirconia |
| Mass fraction (%) | 97 | 3 |
TABLE 10 ingredients of zirconia ceramic slurry (mass fraction%)
The other steps are the same as in example 1, and the product obtained is the same as in example 1.
Example 5
In the method for preparing zirconia ceramic slurry for 3D printing in this example, the components of the ceramic powder and the mass fractions of the components are shown in table 11, and the components of the ceramic slurry and the mass fractions of the components are shown in table 12.
TABLE 11 ingredient table of ceramic powder (mass fraction%)
| Ceramic powder | Submicron zirconia | Nanoscale zirconia |
| Mass fraction (%) | 99 | 1 |
Table 12 components (mass fraction,%) of zirconia ceramic slurry
The other steps were the same as in example 1, and the product obtained was the same as in example 1.
Example 6
In the method for preparing zirconia ceramic slurry for 3D printing in the present example, the components of the ceramic powder and the mass fractions of the components are shown in table 13, and the components of the ceramic slurry and the mass fractions of the components are shown in table 14.
TABLE 13 composition of ceramic powder (mass fraction%)
| Ceramic powder | Submicron zirconia | Nanoscale zirconia |
| Mass fraction (%) | 100 | 0 |
TABLE 14 ingredients of zirconia ceramic slurry (mass fraction,%)
The other steps are the same as in example 1, and the product obtained is the same as in example 1.
And respectively carrying out rheological property test on the ceramic slurry obtained in the above embodiment, and carrying out shrinkage rate test, compactness test, bending strength test, hardness and fracture toughness test and microscopic morphology analysis on a zirconia ceramic blank obtained after 3D printing and sintering.
Slurry rheology test
The rheological property of the slurry is tested by a rotational rheometer Mars60, the diameter of the parallel plate is 40mm, the distance is 1mm, and the testing temperature is 25 ℃. Shear rate when testing steady state rheology of slurriesThe range is set to 0.01 to 100s -1 . When the dynamic rheological property of the slurry is tested, the stress amplitude range is set to be 1-10000 Pa.
The rheological properties of the ceramic slurry may characterize how well it is printable. Through rheological property test on the ceramic slurry, the flow curve and the change rule of the ceramic slurry in several embodiments can be obtained as shown in fig. 2, and it can be seen that the rheological property of the zirconia ceramic slurry can be improved by performing grain composition on ceramic particles, and when the mass ratio of the nanoscale zirconia to the micron-sized zirconia is 5.
Shrinkage test
The sizes (length, width and height) of cuboid samples before and after sintering are measured by a digital vernier caliper, each sample is measured for 5 times, and the linear shrinkage in three directions of the samples is calculated by taking the average value. The calculation formula used is as follows:
in the formula, L 0 、W 0 、H 0 The sizes (mm) of the cuboid sample piece in the three directions of length, width and height before sintering are respectively set; l is 1 、W 1 、H 1 The sizes (mm) of the sintered cuboid sample piece in the three directions of length, width and height are respectively set; Δ L, Δ W, and Δ H are linear shrinkage (%) in the three directions of length, width, and height, respectively. The shrinkage test characterizes the change in size before and after sintering of the ceramic. The shrinkage rates of the sample pieces in different directions in each embodiment are calculated through accurate measurement, and the result is shown in fig. 3, which is beneficial to reserving size shrinkage allowance in the design stage of the sample piece model and improving the size precision of the sintered sample pieceAnd (4) degree.
Relative Density test
The relative density represents the density of the ceramic, and is an important experimental means for researching the influence rule of solid content, sintering temperature and grain composition on the density of the sintered sample. The Archimedes method can be combined with a high-precision electronic balance to accurately calculate the relative density of the sintered sample.
The relative density of the sintered ceramic is tested by adopting an Archimedes method, and the calculation formula is as follows:
in the formula, ρ 1 Is the measured density (g/cm) of the sintered ceramic 3 ) (ii) a D is the relative density (%) of the ceramic after sintering; rho is the theoretical density g/cm of the ceramic 3 ；m 1 And m 2 The mass of the sintered zirconia in air and water, respectively. When the mass percentage of the nano-grade zirconia is 5%, the relative density reaches 99.1%, and the ceramic body reaches the highest density.
Bending strength test
According to GB/T6569-2006 & lt & gt Fine ceramic bending strength test method & gt, an electronic universal tester is adopted to carry out three-point bending test on a ceramic sintering sample, the test sample is processed into 55mm multiplied by 7mm multiplied by 2.5mm, the peripheral surface of the sample is ground and chamfered by a grinding wheel, the test span is 40mm, and the pressurizing rate is 0.5mm/min. The calculation formula of the bending strength is as follows:
wherein σ represents flexural strength (MPa); p is a breaking load (N); l is the test span (mm); w is the width (mm) of the sample piece perpendicular to the load direction; and b is the thickness (mm) of the sample piece parallel to the load direction. The test result is shown in fig. 4, the bending strength of the zirconia ceramic blank prepared by the particle grading method reaches more than 600MPa, is higher than that of the zirconia ceramic blank prepared by the existing zirconia ceramic material extrusion forming method, and meets the international standard and the industrial standard requirements of the dental zirconia ceramic.
Hardness and fracture toughness testing
And measuring the hardness of the sintered ceramic sample by using a Vickers hardness tester, and calculating the fracture toughness of the ceramic sample by using a formula according to the measured hardness and the indentation. During testing, a sintered sample piece is firstly inlaid and sampled, and then the surface of the sample piece is subjected to coarse grinding, fine grinding and polishing treatment until the surface of the sample piece is a mirror surface. Measurement of Vickers hardness H Using a microhardness tester v (GPa), 50N applied force, duration 15s. Estimating the fracture toughness K of the sample by adopting an Evans formula according to the crack length of the indentation IC (MPa·m 1/2 ). The calculation formula for calculating the fracture toughness by the indentation method is as follows:
in the formula, H v Hardness (GPa); a is the initial crack length, i.e. the average length of the indentation diagonal (mm); c is the crack length (mm) after propagation. The calculation result is shown in fig. 5, it can be seen that the fracture toughness of the zirconia ceramic can be significantly improved by adding the nanoscale zirconia, and the fracture toughness is gradually increased along with the increase of the mass ratio of the nanoscale zirconia.
Microscopic topography analysis
The macroscopic physical and mechanical properties of the ceramic are determined by the microstructure such as the pores, the grain size, the grain arrangement condition and the like of the ceramic, and the influence of different grain composition on the microscopic morphology of the sintered section of the zirconia ceramic is observed by adopting a field emission scanning electron microscope and is shown in figure 6. It can be seen that the grain size distribution of the submicron powder zirconia ceramic is relatively narrow, the grain size distribution of the zirconia ceramic after grain grading is wide, and the number of large-size grains is increased along with the increase of the mass ratio of the nano-grade zirconia. When the mass ratio of the nano-grade zirconia is 1%, 3% and 5%, compared with submicron powder zirconia ceramics, the zirconia ceramics after grain grading have tighter grain arrangement, fewer inter-grain pores and higher ceramic density. When the mass percentage of the nano-grade zirconia is 7 percent and 10 percent, a small amount of holes appear on the sintering section, and the density of the ceramic is reduced to some extent. Therefore, the grain size distribution of the zirconia ceramic can be increased by adopting proper grain composition, the inter-grain porosity is reduced, and the ceramic compactness is improved.
The fracture mode of the submicron powder zirconia ceramic can be seen from fracture mode, including intergranular fracture and transgranular fracture, while the fracture mode of the zirconia ceramic after grain composition is mainly transgranular fracture with a small amount of intergranular fracture. Therefore, the zirconia after grain composition has stronger capability of resisting crack propagation and higher fracture toughness.
Although the embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments and the accompanying drawings.
Claims (2)
1. A dental zirconia ceramic slurry for 3D printing, characterized by: comprises solid raw materials, a dispersant, a binder, a plasticizer, a lubricant and a pH regulator;
the solid raw materials comprise the following components in percentage by mass:
submicron zirconia ZrO 2 90%~99%
Nanoscale zirconia ZrO 2 1~10%；
The dispersing agent is sodium polyacrylate;
the adhesive is hydantoin epoxy resin;
the plasticizer is polyethylene glycol;
the lubricant is glycerol;
the pH regulator is sodium hydroxide;
the preparation method of the dental zirconia ceramic slurry for 3D printing is characterized by comprising the following steps: the method comprises the following steps:
1) Grading zirconia: grading the two zirconia powders with different particle sizes according to different mass ratios;
2) Preparing a premixed solution: sequentially adding a dispersant sodium polyacrylate, a binder hydantoin epoxy resin with the content of 3wt%, a plasticizer polyethylene glycol with the content of 0.2wt% and a lubricant glycerol with the content of 0.3wt% into deionized water to prepare a premixed solution of the double-particle-size zirconia ceramic slurry, magnetically stirring the premixed solution at the speed of 60rpm for 20 minutes until the premixed solution is completely dissolved, and dripping a sodium hydroxide solution into the premixed solution to adjust the pH value to 10.8-11.0;
mixing materials: putting two weighed zirconia powder bodies into a ball-milling tank in sequence according to a grading relationship, adding the premixed solution obtained in the step 2), carrying out ball-milling mixing to prepare dual-particle-size zirconia ceramic slurry with the solid content of 58 vol%, taking zirconia balls with the diameter of 10mm as a ball-milling medium, wherein the ball-to-material ratio is 1: and 4, the ball milling rotating speed is 1300r/min, and the ball milling time is 12h.
2. Use of dental zirconia ceramic slurry for 3D printing according to claim 1, characterized in that: the method comprises the following steps:
1) The uniformly mixed zirconia ceramic slurry with different grading relations is filled into a charging barrel, a plunger is pushed by an air pump to extrude the material, the extruding air pressure is adjusted according to the rheological characteristics of different ceramic slurries, so that the diameter of an extruded filament is 1.2 times of the diameter of a printing needle head, the extruded filament is not stretched or wound under the condition that the printing speed is 12mm/s, the diameter of the printing needle head is selected to be 0.5mm, and the thickness of the layer is 1.2 times of the diameter of the printing needle head;
2) Drying the printed ceramic sample piece for 24 hours at room temperature, then placing the ceramic sample piece into a box furnace for degreasing and sintering, firstly heating the dried ceramic sample piece to 600 ℃ at the heating rate of 2 ℃/min for degreasing, degreasing for 1 hour, then heating to 1550 ℃ at the heating rate of 3 ℃/min for sintering, after sintering for 2 hours, cooling to 500 ℃ at the cooling rate of 3 ℃/min, finally cooling to room temperature along with the furnace, manually polishing and polishing the sintered blank body for use, and printing the prepared ceramic slurry into a tooth blank by an extrusion process, wherein a 3D printer is a 3D printing platform provided with a micro-flow extrusion molding head device.
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