CN111072382B - Zirconia ceramic block for all-ceramic false tooth and preparation process thereof - Google Patents

Zirconia ceramic block for all-ceramic false tooth and preparation process thereof Download PDF

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CN111072382B
CN111072382B CN201811214732.5A CN201811214732A CN111072382B CN 111072382 B CN111072382 B CN 111072382B CN 201811214732 A CN201811214732 A CN 201811214732A CN 111072382 B CN111072382 B CN 111072382B
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ink
powder
ceramic block
layer
color
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CN111072382A (en
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乔学斌
李亚东
李亚军
朱阳光
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Suzhou Dingan Technology Co ltd
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Abstract

The invention provides a zirconia ceramic block for a full-ceramic denture and a preparation process thereof, belonging to the technical field of ceramic materials for dentistry. The color and/or transmittance of the zirconia ceramic block for the complete ceramic false tooth are changed in a multi-layer quasi-continuous gradient manner from one side to the other side of a determined direction. The zirconia ceramic block for the full-ceramic false tooth is prepared by adopting an ink-jet additive printing technology, and is formed by periodically spreading powder layer by layer along a determined direction by taking partially stabilized zirconia powder as a raw material and selectively performing ink-jet printing and superposition layer by adopting white ink and/or colored ink with different solute concentrations and/or anti-reflection ink. The ink-jet additive printing technology adopted by the invention has the advantages of high forming speed, realization of mass production, individuation customization, stable performance of the produced product, complete elimination of the defects of the zirconia ceramic block for the existing all-ceramic false tooth, hardness change of color and/or light transmittance, unnatural and vivid property and the like, and satisfaction of aesthetic repair requirements of the all-ceramic false tooth.

Description

Zirconia ceramic block for all-ceramic false tooth and preparation process thereof
Technical Field
The invention relates to the technical field of dental ceramic materials, in particular to a zirconia ceramic block for an all-ceramic denture with quasi-continuous change of color and/or light transmittance and a preparation process thereof.
Background
The CAD/CAM technology is adopted to manufacture the full-ceramic denture prosthesis, and the full-ceramic denture prosthesis is widely applied to the field of oral repair. The zirconia ceramic block for the full-ceramic denture is a main material for manufacturing the full-ceramic denture prosthesis due to good biocompatibility, high obdurability, excellent wear resistance and stability of physicochemical property. In prosthodontics, the color gradation and translucency of zirconia ceramic blocks for full-ceramic dentures are important indicators that affect the consistency of full-ceramic denture restorations and natural teeth. However, most of the zirconia ceramic blocks for the commercially available all-ceramic denture are white, so that to produce an all-ceramic denture prosthesis which is natural and vivid and has better layering effect, color-masking porcelain must be used and the thickness of facing porcelain must be increased. However, the existing zirconia ceramic block for the full-ceramic denture and the artificial modification technology have limitations on the repair of the full-ceramic denture, and cannot obtain the aesthetic characteristics of natural teeth, so that a new material and a new process are urgently needed to be searched.
At present, the aesthetic restoration method of the full-ceramic false tooth commonly used in the industry is to color the full-ceramic false tooth inner crown so as to ensure that the color of the full-ceramic false tooth inner crown is closer to that of natural teeth. The traditional coloring technology of the full-ceramic denture inner crown mainly comprises an internal coloring method and an external coloring method, wherein the internal coloring method is to firstly produce a zirconium oxide ceramic block for a colored full-ceramic denture by adding coloring oxides, and then to sinter the zirconium oxide ceramic block into the colored full-ceramic denture inner crown by adopting the CAD/CAM technology, but the obtained denture inner crown has single color and no layering; the external dyeing method is to process the zirconia porcelain block for the white all-ceramic false tooth into an all-ceramic false tooth inner crown blank, then soak and brush the blank with dyeing (coloring) liquid, and sinter the blank after drying into a colored all-ceramic false tooth inner crown. Although the two methods have simple processes and can simulate the color of natural teeth to a certain extent, the produced colored full-ceramic denture inner crown is easy to have the problems of uneven dyeing, unnatural color change and the like, so that the colored full-ceramic denture inner crown still needs to be glazed, and the colored full-ceramic denture inner crown and the facing porcelain have low bonding strength, so that porcelain collapse is easy to occur, and finally the repair failure is caused. Meanwhile, the traditional coloring technology cannot simultaneously meet the requirement of the aesthetic restoration of the full-ceramic false tooth on the change of the color and the light transmittance of the restoration in clinic.
In order to make the dyed full-ceramic denture have gradient color and light transmittance and more approximate to the aesthetic characteristics of natural teeth, CN104337586A discloses a dental model gradient-layer ceramic block and a manufacturing method thereof, wherein the color gradient is realized by respectively immersing two surfaces of a zirconium oxide ceramic block blank for a round full-ceramic denture into different dyeing solutions and capillary penetration. The technology has the defects of long dyeing time, complex process, complexity and the like, is difficult to control the uniform gradient degree of the color, has poor stability and consistency of products, and can not meet the personalized customization requirement of gradient of the color and the light transmittance of the all-ceramic denture.
In order to simplify or cancel the external dyeing process of the full-ceramic false tooth blank and enable the full-ceramic false tooth produced by the internal dyeing method to have gradual change color and gradient light transmission, CN105584161A provides a color zirconia material with gradually changed light transmission, which solves the problems of complicated dyeing procedure, unstable coloring performance and the like in the later stage of the production of the full-ceramic false tooth blank and meets the requirement of the tooth cut end on the light transmission. The method comprises the steps of layering prefabricated powder prepared by mixing three kinds of powder, namely 3Y-TZP, 3.5-4.5Y-PSZ and 4.5-6Y-PSZ, with a colorant according to different mass ratios, placing the prefabricated powder into a die cavity, carrying out dry pressing and cold isostatic pressing to obtain a zirconium oxide ceramic block blank for the all-ceramic false tooth with the light-transmittance gradient color five-layer structure, placing the blank into a sintering furnace for pre-sintering, and carrying out cutting and secondary sintering to obtain the light-transmittance gradient color all-false tooth ceramic. The patent can obtain the zirconia ceramic block for the full-ceramic false tooth with gradation change of color and light transmission, but the forming process is complex, the thickness of each layer is larger, the range of the gradation change of the color and the light transmission is large, and the color and the light transmission change hard, discordant and unnatural. Meanwhile, the powder spreading thickness cannot be ensured to be uniform during dry pressing, and friction force exists between the wall of the forming die cavity and the powder, so that interfaces among layers in a formed blank are easy to bend, the variation trends of color and light transmittance are different in different areas, and the stability and consistency of the color and light transmittance of a product are poor. In order to solve the problems, CN104909745A discloses a method for preparing a uniformly-graded zirconia ceramic block, which adopts a mode of combining an internal dyeing method and an external dyeing method, and firstly, CeO is weighed2、Fe2O3、ZrO2、Y2O3、Pr6O11And Er2O3The method comprises the steps of preparing raw materials to obtain the zirconium oxide ceramic block for the all-ceramic false tooth with uniform internal dyeing, and then soaking the zirconium oxide ceramic block for the all-ceramic false tooth with uniform and gradual change of color by adopting dyeing liquid to finally obtain the zirconium oxide ceramic block for the all-ceramic false tooth with uniform and gradual change of color. The technology can obtain the oxidation of the complete porcelain false tooth with more uniform coloring and continuous color changeHowever, the zirconium porcelain block still has the disadvantages of complex process, high difficulty in controlling the external dyeing process, incapability of simultaneously obtaining natural aesthetic effects of color individuation and gradient change of light transmittance, and unsatisfactory stability and consistency of product performance.
Theoretically, the more layers are arranged in the production process of the zirconia ceramic block for the all-ceramic false tooth, the smaller the thickness of each layer is, the closer the color or light transmittance is to nature, but in the aspect of a forming process, the more layers are added, so that the processing difficulty and cost are increased, and the thickness of each layer cannot be further reduced by utilizing the prior art to meet the preparation requirements of more layers. Therefore, at present, the full-ceramic denture zirconia ceramic block with both color and light transmittance and quasi-continuous or continuous gradient change cannot be produced, and a process method which has simple process and can ensure stable and consistent product performance and can custom-manufacture the full-ceramic denture zirconia ceramic block cannot be provided. The development of zirconia ceramic blocks for fully ceramic dentures having quasi-continuous variations in color (color saturation) and light transmittance remains a technical problem and a focus of research faced by those skilled in the art.
Disclosure of Invention
The invention aims to provide a zirconia ceramic block for a full-ceramic denture with quasi-continuous change of color (color saturation) and/or light transmittance and a preparation process thereof. The invention not only can solve the problems that the whole color and the light transmittance of the existing full-ceramic denture prosthesis are single, the later dyeing procedure is complicated, the production process in the production process of the zirconia ceramic block for the existing multilayer light transmittance gradient colored full-ceramic denture is complicated, the thickness of each layer is large, the color and the light transmittance change in a hierarchical way, and the color and the light transmittance change are hard, uncoordinated and unnatural; the special requirements of the full-ceramic denture cutting end on quasi-continuous gradient change of light transmittance and color (color saturation) can be met, the change rule of the color and the light transmittance of natural teeth can be simulated, the change is smooth and natural, the physical and chemical properties of the product are consistent and stable, the product can be accurately controlled and customized individually, the preparation process is simple, and the operation is convenient.
In order to achieve the aim, the invention also relates to an ink-jet additive printing process of the zirconium oxide ceramic block for the full-ceramic false tooth, wherein the color (color saturation) and the light transmittance are quasi-continuously changed. The Inkjet additive Printing process can be called a Three-Dimensional Printing bonding forming method (Three Dimensional Printing and blending, abbreviated as 3DP), namely Inkjet deposition, can also be called adhesive Jetting (Binder Jetting) and Inkjet Powder Printing (Inkjet Powder Printing), and belongs to a liquid jet Printing forming process.
According to the zirconia ceramic block for the all-ceramic denture, each layer which is sequentially arranged from bottom to top has quasi-continuous gradient-changing color and/or light transmittance, and different coloring inks are selected according to the personalized application requirements and the color change based on Vita16, Vita 26 or Vita3D-Master colorimetric plates; carrying out data processing by a computer to form two-dimensional printing section data of the porcelain block blank, printing parameter generation and process control; the range of the transmittance is such that the transmittance at a measurement wavelength of 600nm or 800nm is 5% to 70% when the sample thickness is 1 mm. Each layer of the zirconia ceramic block for the all-ceramic false tooth adopts yttria (Y)2O3) Cerium oxide (CeO)2) Magnesium oxide (MgO), scandium oxide (Sc)2O3) Samarium oxide (Sm)2O3) Ytterbium oxide (Yb)2O3) And/or calcium oxide (CaO) stabilizers2) The powder is used as a raw material and is formed by spreading the powder along a determined direction and superposing the powder layer by layer in ink-jet printing. The thickness of each layer of the zirconia ceramic block for the complete ceramic false tooth is 5-500 μm by powder spreading and ink-jet printing along the vertical direction of each layer.
Under the control of a system, a layer of powder is uniformly laid on each powder box on a working platform, an ink-jet printing head can move along the X-axis direction and the Y-axis direction, and according to two-dimensional printing section data obtained by model slicing, blank ink and/or coloring ink and/or anti-reflection ink are selectively sprayed respectively, simultaneously or alternately, and finally, a plane pattern is printed, so that the powder in the plane pattern is solidified. After the printing of the single two-dimensional printing section pattern is finished, the working platform descends by a distance of one printing layer thickness unit, the powder box performs powder paving and leveling operation again, and the ink-jet printing head performs the printing operation of the two-dimensional printing section pattern again. And (3) spreading powder and ink-jet printing in such a way repeatedly, and finally completing the printing of the zirconium oxide ceramic block blank for the all-ceramic false tooth with the quasi-continuous change of color and/or light transmittance. After the blank body is printed, taking out the zirconia ceramic block blank body for the all-ceramic false tooth, cleaning floating powder on the surface of the blank body, and carrying out cold isostatic pressing after the blank body is subjected to vacuum plastic packaging and packaging; placing the cold isostatic pressing blank into a box-type electric furnace, slowly heating to degrease and presintering to obtain a pre-sintered ceramic block; finally, according to the product specification requirements, the zirconia ceramic block for the full-ceramic false tooth with the color (color saturation) and/or the light transmittance quasi-continuous change along a determined direction is obtained by machining.
The preparation method of the zirconia ceramic block for the all-ceramic denture specifically comprises the following steps: firstly, according to the specific requirement of quasi-continuous change of color and/or light transmittance of a zirconia ceramic block for a complete porcelain false tooth, selecting a blank ink and/or one or more coloring inks with different solute concentrations and/or one or more anti-reflection inks with different solute concentrations, and adopting a single ink-jet printing head or a plurality of ink-jet printing heads, wherein one ink supply box of each ink-jet printing head is filled with the blank ink or the coloring ink or the anti-reflection ink according to the requirement; at the same time, one or more kinds of yttrium oxide (Y) with different contents are selected according to the requirement2O3) Cerium oxide (CeO)2) Magnesium oxide (MgO), scandium oxide (Sc)2O3) Samarium oxide (Sm)2O3) Ytterbium oxide (Yb)2O3) And/or calcium oxide (CaO) stabilizers2) The powder is filled into one or more powder boxes respectively or in a mixed manner according to different oxide types or contents; determining the powder spreading sequence of each powder box, the single descending stroke of the working platform, the powder spreading thickness of each layer and the ink jet printing parameters of each layer of permeation ink and/or coloring ink and/or blank ink.
The powder can be uniformly spread and scraped on the working platform by moving the powder boxes on the guide rail in turn, then the ink-jet printing head prints respectively or simultaneously or alternatively according to the two-dimensional printing section pattern of the zirconium oxide ceramic block blank for the complete ceramic false tooth, the coloring ink and/or the anti-reflection ink and/or the blank ink jetted by the ink-jet printing head enables the partial stabilized zirconium oxide powder layer to be solidified according to the two-dimensional printing section pattern, after the ink-jet printing of one layer is completed, the working platform descends a stroke of the thickness of the printing layer, and a computer program controls one powder box to move, spread and scrape the powder again, then the ink-jet printing head prints the ink again, and the steps are repeated continuously until the printing of the whole thickness of the zirconium oxide ceramic block blank for the complete ceramic false tooth with quasi-continuous change of color and/or light transmittance is completed.
In order to obtain a zirconia ceramic block for an all-ceramic denture with quasi-continuous changes of color (color saturation) and light transmittance, the adopted ink-jet additive manufacturing technology comprises the following steps:
(1) using one or more kinds of yttrium oxide (Y) with different mole percentages2O3) Cerium oxide (CeO)2) Magnesium oxide (MgO), scandium oxide (Sc)2O3) Samarium oxide (Sm)2O3) Ytterbium oxide (Yb)2O3) And/or calcium oxide (CaO) stabilizer as a main preparation raw material of a zirconia ceramic block for a full ceramic denture; one or more CeO with different concentrations are adopted2、Fe2O3、Mn2O3、Pr2O3、Er2O3、TiO2、GeO2、ZrO2、Al2O3、CaO、CuO、Co3O4、NiO、V2O5、Cr2O3、In2O3、Dy2O3、Eu2O3、Ga2O3、Ho2O3、Tb2O3、RuO2、SnO2、Bi2O3And/or Tm2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders, or containing various concentrations of Ce4+、Fe3+、Mn3+、Pr3+、Er3+、Ti4+、Ge4+、Zr4 +、Al3+、Ca2+、Cu2+、Co2+、Co3+、Ni2+、V5+、Cr3+、In3+、Dy3+、Eu3+、Ga3+、Ho3+、Tb3+、Ru4+、Sn4+、Bi3+And/or Tm3+Ionic aqueous, non-aqueous or photocurable solutions as coloring inks; one or more than one of Y with different concentrations2O3、La2O3、Sc2O3、Nd2O3、Yb2O3、Gd2O3、Sm2O3、Mn2O3、Er2O3、ThO2、TiO2、CeO2MgO, CaO and/or Al2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders, or various concentrations Y3+、La3+、Sc3+、Nd3+、Yb3+、Gd3+、Sm3+、Mn3+、Er3+、Th4+、Ti4+、Ce4+、Mg2+、Ca2+And/or Al3+Ionic aqueous, non-aqueous or photocurable solutions as antireflective inks; adopting a mixed solution which does not contain any nano metal oxide powder and/or any metal ions and only contains aqueous, non-aqueous or photo-curing binder, humectant, quick drying agent, lubricant, coagulant, flow increasing agent, defoaming agent and pH regulator as blank ink;
(2) filling a blank ink into a special 0# ink box;
(3) one or more than one coloring ink is put into 1 ink box or a plurality of ink boxes respectively;
(4) one or more anti-reflection ink is put into 1 ink box or a plurality of ink boxes respectively;
(5) one or more than one partially stabilized zirconia powder is put into 1 powder box or a plurality of powder boxes respectively;
(6) according to the gradient requirement (different product models) of quasi-continuous change of color (color saturation) and/or light transmittance and the specification size (namely the two-dimensional printing section size and the thickness H of a product), determining the two-dimensional printing section size, the single descending stroke of a working cylinder lifting platform (working platform for short) or the thickness (H) of an ink-jet printing layer, calculating the total number (N is H/H) of the ink-jet printing layer, and driving at least 1 box of powder to spread powder along the horizontal direction by a linear motor and leveling the powder by a scraper;
(7) determining the type and concentration of the permeation-enhanced ink and/or the coloring ink and/or the blank ink, the number of the used inks and ink-jet printing parameters according to the gradient requirement of quasi-continuous change of color (color saturation) and/or light transmittance, such as: pixel DPI (ink jet dots distributed on each inch of the two-dimensional printing section, 0 × 0-2880 × 2880DPI) and single-layer repeated printing times PASS (the times of ink repeated covering and printing on the two-dimensional printing section of single-layer powder are 1-15 times);
(8) according to the gradient requirement of quasi-continuous change of the color (color saturation) and/or the light transmittance of the zirconia ceramic block for the complete porcelain denture, based on the adopted blank ink and/or the anti-reflection ink and/or the coloring ink with various types and concentrations and the set ink-jet printing parameters, according to the single-layer thickness (h) of the printing layer of the zirconia ceramic block for the complete porcelain denture and the dimension of the two-dimensional printing section, the linear motor drives the ink-jet printing head to move forward and spray the blank ink, the anti-reflection ink and/or the coloring ink with various types and concentrations respectively or simultaneously or alternatively, powder is selectively paved along the vertical direction of the two-dimensional printing section in sequence and the ink-jet printing is selectively carried out layer by layer according to the set two-dimensional printing section, after one layer of printing is completed, the working platform descends by a printing layer thickness (H), and then powder spreading and ink jet printing are carried out in a circulating and alternating mode until the printing of N layers (total thickness H) of the whole product is completed;
(9) after the N-layer ink-jet printing is finished, taking out the printed zirconium oxide porcelain block blank for the all-porcelain false tooth, cleaning floating powder on the surface of the blank, carrying out cold isostatic pressing and reshaping after the blank is subjected to vacuum plastic packaging, wherein the relative density of the blank exceeds 50%;
(10) putting the zirconium oxide ceramic block blank for the full-ceramic denture after cold isostatic pressing reshaping into a box-type electric furnace, slowly heating for degreasing and presintering;
(11) according to the product specification requirements, the zirconium oxide ceramic block for the complete ceramic false tooth with the color (color saturation) and/or the light transmittance quasi-continuous change along a determined direction is obtained after machining.
The yttrium oxide (Y) with different contents adopted by the invention2O3) Cerium oxide (CeO)2) Magnesium oxide (MgO), scandium oxide (Sc)2O3) Samarium oxide (Sm)2O3) Ytterbium oxide (Yb)2O3) And/or calcium oxide (CaO) stabilizers2) The powder has a particle size of 0.01 to 200 μm and an irregular or spherical particle morphology. Irregular particles and/or spherical particles with the particle sizes of 0.01-0.1 mu m, 0.1-1 mu m, 1-10 mu m, 10-50 mu m, 50-100 mu m and 100-200 mu m are mixed according to different volume proportions to prepare the special mixed powder for the ink-jet additive printing of the zirconia ceramic block blank for the all-ceramic denture with the particle sizes distributed in multiple stages. The irregular particles and/or spherical particles in the partially stabilized zirconia powder are formed by combining nano-crystalline grains, and the size of the nano-crystalline grains is 5-200 nm.
Partially stabilized zirconia (ZrO) used2) The total content of stabilizer in the powder is less than 30 mol%, wherein the yttrium oxide (Y)2O3) 0 mol% -8 mol% of cerium oxide (CeO)2) 0 to 30 mol% of magnesium oxide (MgO), 0 to 15 mol% of scandium oxide (Sc)2O3) 0 to 15 mol% of samarium oxide (Sm)2O3) 0 to 15 mol% of ytterbium oxide (Yb)2O3) The content is 0-15 mol% and/or the content of calcium oxide (CaO) is 0-18 mol%, and the specific proportion is selected and adjusted according to the specific requirements on quasi-continuous change of light transmittance and highest light transmittance.
The used coloring ink can be aqueous, non-aqueous suspension or light-cured resin suspension containing mixed powder of multiple nano oxides, wherein CeO2、Fe2O3、Mn2O3、Pr2O3、Er2O3、TiO2、GeO2、ZrO2、Al2O3、CaO、CuO、Co3O4、NiO、V2O5、Cr2O3、In2O3、Dy2O3、Eu2O3、Ga2O3、Ho2O3、Tb2O3、RuO2、SnO2、Bi2O3And/or Tm2O3The content of the nano powder is 0.000001 wt% -10 wt%, the particle size of each nano metal oxide powder is 10-100 nm, and the particle shape is irregular and/or spherical. The specific composition and content can be selected and adjusted according to the quasi-continuous change of the color (color saturation) and the color attribute requirement of the zirconia ceramic block for the complete porcelain denture.
The coloring ink used may contain various concentrations of Ce4+、Fe3+、Mn3+、Pr3+、Er3+、Ti4+、Ge4+、Zr4+、Al3+、Ca2+、Cu2+、Co2+、Co3+、Ni2+、V5+、Cr3+、In3+、Dy3+、Eu3+、Ga3+、Ho3+、Tb3+、Ru4+、Sn4+、Bi3+And/or Tm3+An aqueous solution, a non-aqueous solution or a photocurable resin solution of ions, wherein the solubility of each metal ion is 5 to 100000 ppm. The specific composition and content are selected and adjusted according to the requirements of the zirconia ceramic block for the complete porcelain denture on quasi-continuous gradient change of color (color saturation) and color attribute.
The anti-reflection ink can be aqueous or non-aqueous suspension or light-cured resin suspension containing multiple mixed nano-oxide powders, wherein Y is2O3、La2O3、Sc2O3、Nd2O3、Yb2O3、Gd2O3、Sm2O3、Mn2O3、Er2O3、ThO2、TiO2、CeO2MgO, CaO and/or Al2O3The content of the nano metal oxide powder is 0.000001 wt% -10 wt%, the particle size of each nano metal oxide powder is 10-100 nm, and the particle shape is irregular and/or spherical. Specific composition and contentThe selection and adjustment are made according to the quasi-continuous variation of transmittance and the highest transmittance requirement of the zirconia ceramic block for the complete porcelain denture.
The anti-reflection ink adopted can also contain various concentrations of Y3+、La3+、Sc3+、Nd3+、Yb3+、Gd3+、Sm3+、Mn3+、Er3+、Th4+、Ti4+、Ce4+、Mg2+、Ca2+And/or Al3+An aqueous solution, a non-aqueous solution or a photocurable resin solution of ions, wherein the concentration of each metal ion is 5 to 100000 ppm. The specific composition and content are selected and adjusted according to the quasi-continuous change of the transmittance and the highest transmittance requirement of the zirconia ceramic block for the complete porcelain false tooth.
The adopted blank ink is an aqueous, non-aqueous or photocurable solution which does not contain any nano metal oxide powder and any metal ions, but contains a binder, a humectant, a quick drying agent, a lubricant, a coagulant, a flow increasing agent, a defoaming agent and a pH regulator, wherein the pH value of the aqueous, non-aqueous or photocurable solution is 5-9, and the viscosity of the aqueous, non-aqueous or photocurable solution is 1-500 mPa · s.
The blank ink, the anti-reflection ink and the colored ink all contain aqueous, non-aqueous or photo-curing binder, humectant, quick drying agent, lubricant, coagulant, flow increasing agent, defoaming agent and pH regulator; the blank ink, the anti-reflection ink and the coloring ink can be water-based, non-water-based or photocuring liquid, the pH value is 5-9, and the viscosity is 1-500 mPa & s.
Wherein, the preferred technical scheme is as follows:
in the step (6), the thickness of each layer is 5-500 μm;
in the step (9), the cold isostatic pressing remolding pressure is 50-350 MPa;
in the step (10), the temperature rising speed is less than 1 ℃/min, the degreasing temperature is 200-650 ℃, the heat preservation time is 3-10 h, the pre-sintering temperature is 850-1200 ℃, the heat preservation time is 1-5 h, and the temperature reduction speed is less than 1 ℃/min.
The invention has the following beneficial effects:
the zirconia ceramic block for the all-ceramic denture produced by adopting the technology can simulate the change rule of the color and the light transmittance of the natural tooth without the existing external dyeing or internal dyeing process, and when the all-ceramic denture prosthesis is manufactured, the special requirements of the all-ceramic denture on the natural change of the color and the light transmittance can be met, and the application of the color-masking porcelain and the decorative porcelain can be cancelled, so that the clinical doctor can reduce the preparation amount of the tooth body to the maximum extent, the tooth body tissue of the patient is preserved, and the pain of the patient is relieved; because a technician is not required to carry out complicated dyeing or anti-reflection modification, the processing process of the all-ceramic denture is simplified, the production efficiency is improved, the defects of unnatural light transmission, uneven color or transitional hardening and the like of the existing all-ceramic denture cutting end can be eliminated, and the aesthetic and personalized repairing effects of the all-ceramic denture are achieved. Meanwhile, the ink-jet additive technology is adopted to produce the zirconia ceramic block blank for the all-ceramic false tooth with the quasi-continuous change of the color and/or the light transmittance, the forming speed is high, the mass production can be realized, the process repeatability is good, the performance is stable, the color (color saturation) and/or the quasi-continuous change effect of the light transmittance can be obtained by reasonably adjusting the ink-jet printing parameters, and the color and the light transmittance change of the zirconia ceramic block for the all-ceramic false tooth are more natural and vivid. Meanwhile, the zirconium oxide ceramic block for the full-ceramic false tooth produced by the technology can ensure that the physical and chemical properties are consistent, stable, accurate and controllable, meet the requirements of personalized customization of quasi-continuous change of color and light transmittance, further reduce the comprehensive operation cost of production and preparation and the like.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a zirconia ceramic block for a fully ceramic denture.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments shown in the drawings. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention.
One embodiment of the present invention is provided below:
the zirconia ceramic block for the all-ceramic false tooth is formed by adopting partially stabilized zirconia powder as a raw material, periodically spreading the powder layer by layer along a determined direction, selectively and respectively or simultaneously or alternately carrying out ink-jet printing and superposition layer by adopting white ink and/or coloring ink with different solute concentrations and/or anti-reflection ink with different solute concentrations, and the color and/or the light transmittance of the zirconia ceramic block for the all-ceramic false tooth are quasi-continuously changed from one side to the other side of the determined direction.
Furthermore, the determined direction is the thickness direction of the powder paving, the determined direction is vertical to the powder paving direction of each layer, the color (color saturation) changes from dark color to light color quasi-continuously and gradiently from one side to the other side along the determined direction) and/or the light transmittance changes from 5% to 70% quasi-continuously, and the thickness of each layer of the powder paving is 5-500 mu m.
Further, the partially stabilized zirconia powder is prepared by mixing irregular particles and/or spherical particles with the sizes of 0.01-0.1 mu m, 0.1-1 mu m, 1-10 mu m, 10-50 mu m, 50-100 mu m and 100-200 mu m according to different proportions, the particle sizes are distributed in a multistage manner, the irregular particles and/or the spherical particles are formed by combining nano crystal grains, and the crystal grain sizes are 5-200 nm.
Further, the partially stabilized zirconia powder optionally employs an oxide as a stabilizer, the oxide being one or more of yttria, ceria, magnesia, scandia, samaria, ytterbia and/or calcia.
Furthermore, the total content of the stabilizers in the partially stabilized zirconia powder is less than 30 mol%, wherein the content of yttrium oxide is 0 mol% to 8 mol%, the content of cerium oxide is 0 mol% to 30 mol%, the content of magnesium oxide is 0 to 15 mol%, the content of scandium oxide is 0 to 15 mol%, the content of samarium oxide is 0 to 15 mol%, the content of ytterbium oxide is 0 to 15 mol% and/or the content of calcium oxide is 0 to 18 mol%.
Furthermore, the anti-reflection ink and the coloring ink contain nano oxide powder and/or metal ions, and also contain aqueous, non-aqueous or photocurable binding agent, humectant, quick drying agent, lubricant, coagulant, flow promoter, defoaming agent and pH regulator, wherein the pH values of the anti-reflection ink and the coloring ink are both 5-9, and the viscosities of the anti-reflection ink and the coloring ink are both 1-500 mPa & s.
Further, the blank ink does not contain any nano oxide powder and/or any metal ions, but contains a water-based, non-water-based or photo-curing binder, a humectant, a quick drying agent, a lubricant, a coagulant, a flow increasing agent, an antifoaming agent and a pH regulator, and has a pH value of 5-9 and a viscosity of 1-500 mPas.
Further, with a composition containing CeO2、Fe2O3、Mn2O3、Pr2O3、Er2O3、TiO2、GeO2、ZrO2、Al2O3、CaO、CuO、Co3O4、NiO、V2O5、Cr2O3、In2O3、Dy2O3、Eu2O3、Ga2O3、Ho2O3、Tb2O3、RuO2、SnO2、Bi2O3And/or Tm2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders or containing Ce4+、Fe3+、Mn3+、Pr3+、Er3+、Ti4+、Ge4+、Zr4+、Al3+、Ca2+、Cu2+、Co2+、Co3+、Ni2+、V5+、Cr3+、In3+、Dy3+、Eu3+、Ga3+、Ho3+、Tb3+、Ru4+、Sn4+、Bi3+And/or Tm3+Ionic aqueous, non-aqueous or photocurable solutions as coloring inks; by using a compound containing Y2O3、La2O3、Sc2O3、Nd2O3、Yb2O3、Gd2O3、Sm2O3、Mn2O3、Er2O3、ThO2、TiO2、CeO2MgO, CaO and/or Al2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders or containing Y3+、La3+、Sc3+、Nd3+、Yb3+、Gd3+、Sm3+、Mn3+、Er3 +、Th4+、Ti4+、Ce4+、Mg2+、Ca2+And/or Al3+The ionic aqueous, non-aqueous or light-cured solution is used as anti-reflection ink, the particle size of nano metal oxide powder used by the coloring ink and the anti-reflection ink is less than 100nm, and the metal ions used by the coloring ink and the anti-reflection ink are derived from one or more of chloride, nitrate, carbonate, sulfate, acetate, glutarate, malate, gluconate, fumarate, oxalate, lactate and citrate.
Still further, CeO in the colored ink2、Fe2O3、Mn2O3、Pr2O3、Er2O3、TiO2、GeO2、ZrO2、Al2O3、CaO、CuO、Co3O4、NiO、V2O5、Cr2O3、In2O3、Dy2O3、Eu2O3、Ga2O3、Ho2O3、Tb2O3、RuO2、SnO2、Bi2O3And/or Tm2O3The content of the nano metal oxide powder is 0.000001 to 10 weight percent respectively or Ce in the colored ink4+、Fe3+、Mn3+、Pr3+、Er3+、Ti4+、Ge4+、Zr4+、Al3+、Ca2+、Cu2+、Co2+、Co3+、Ni2+、V5+、Cr3+、In3+、Dy3+、Eu3+、Ga3+、Ho3+、Tb3+、Ru4+、Sn4+、Bi3+And/or Tm3+The ion solubility is 5 to 100000 ppm.
Still further, enhancing Y in the ink2O3、La2O3、Sc2O3、Nd2O3、Yb2O3、Gd2O3、Sm2O3、Mn2O3、Er2O3、ThO2、TiO2、CeO2MgO, CaO and/or Al2O3The content of the nano metal oxide powder is 0.000001 wt% -10 wt% respectively; or Y in antireflective inks3+、La3+、Sc3+、Nd3+、Yb3+、Gd3+、Sm3+、Mn3+、Er3+、Th4+、Ti4+、Ce4+、Mg2 +、Ca2+And/or Al3+The ion solubility is 5 to 100000 ppm.
Referring to fig. 1, a process for preparing a zirconia ceramic block for an all-ceramic denture, which comprises the steps of periodically spreading partially stabilized zirconia powder layer by layer along a certain direction as a raw material, selectively performing inkjet printing and superposition on the powder layer by layer or simultaneously or alternately by layer by using white ink and/or coloring ink with different solute concentrations and/or anti-reflection ink with different solute concentrations, and preparing a zirconia ceramic block blank for an all-ceramic denture, wherein the color and/or the light transmittance of the zirconia ceramic block blank for an all-ceramic denture are quasi-continuously changed from one side to the other side of the certain direction.
Further, the zirconia ceramic block for the complete ceramic false tooth with the quasi-continuous change of color and/or light transmittance is prepared by adopting an ink-jet additive manufacturing technology, and the preparation process comprises the following steps:
(1) one or more partially stabilized zirconia powders containing different mole percentages of yttria, ceria, magnesia, scandia, samaria, ytterbia and/or calcium oxide stabilizers are used as main preparation raw materials of the zirconia ceramic block for the full-ceramic false tooth; one or more CeO with different concentrations are adopted2、Fe2O3、Mn2O3、Pr2O3、Er2O3、TiO2、GeO2、ZrO2、Al2O3、CaO、CuO、Co3O4、NiO、V2O5、Cr2O3、In2O3、Dy2O3、Eu2O3、Ga2O3、Ho2O3、Tb2O3、RuO2、SnO2、Bi2O3And/or Tm2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders, or containing varying concentrations of Ce4+、Fe3+、Mn3+、Pr3+、Er3+、Ti4+、Ge4+、Zr4+、Al3+、Ca2+、Cu2+、Co2+、Co3+、Ni2+、V5 +、Cr3+、In3+、Dy3+、Eu3+、Ga3+、Ho3+、Tb3+、Ru4+、Sn4+、Bi3+And/or Tm3+Ionic aqueous, non-aqueous or photocurable solutions as coloring inks; one or more than one of Y with different concentrations2O3、La2O3、Sc2O3、Nd2O3、Yb2O3、Gd2O3、Sm2O3、Mn2O3、Er2O3、ThO2、TiO2、CeO2MgO, CaO and/or Al2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders, or different concentrations Y3+、La3+、Sc3+、Nd3+、Yb3+、Gd3+、Sm3+、Mn3+、Er3+、Th4+、Ti4 +、Ce4+、Mg2+、Ca2+And/or Al3+Ionic aqueous, non-aqueous or photocurable solutions as antireflective inks;
(2) filling blank ink which does not contain any nano oxide powder and/or any metal ions and contains aqueous, non-aqueous or photo-curing binder and humectant, quick drying agent, lubricant, coagulant, flow promoter, defoaming agent and pH regulator into 1 special ink box;
(3) one or more than one coloring ink is put into 1 ink box or a plurality of ink boxes respectively;
(4) one or more anti-reflection ink is put into 1 ink box or a plurality of ink boxes respectively;
(5) one or more than one kind of partially stabilized zirconia powder is put into 1 powder box or respectively put into a plurality of powder boxes;
(6) according to the gradient requirement of quasi-continuous change of the color and/or the light transmittance of a product and the specification and the size of the product, determining the size of a two-dimensional printing section, the single descending stroke of a working platform or the thickness of an ink-jet printing layer, calculating the total number of the ink-jet printing layers, and driving at least 1 powder box to spread powder along the horizontal direction by a linear motor and leveling the powder by a scraper;
(7) determining the solute type and concentration of the permeation ink and/or the coloring ink and/or the blank ink, the number of ink boxes and ink-jet printing parameters according to the gradient requirement of quasi-continuous change of color and/or light transmittance;
(8) according to the gradient requirement of quasi-continuous change of color and/or light transmittance of the zirconia ceramic block for the full-ceramic denture, based on the adopted blank ink and/or anti-reflection ink and/or coloring ink with various solute types and concentrations, the number of ink boxes and set ink-jet printing parameters, according to the single-layer thickness and the two-dimensional printing section size of the printing layer of the zirconia ceramic block blank for the full-ceramic denture, a linear motor drives an ink-jet printing head to move forward and spray the blank ink and/or anti-reflection ink and/or coloring ink with various solute types and concentrations, powder is selectively paved in the vertical direction of the two-dimensional printing section in sequence, and ink-jet printing is selectively and respectively or simultaneously or alternately carried out layer by layer according to the set two-dimensional printing section, after one-layer printing is completed, a stroke of the thickness of the printing layer is reduced by a working platform, and then powder paving and ink-jet printing are carried out in a circulating and alternating manner, until finishing printing all layers of the whole product;
(9) after the ink-jet printing is finished, taking out the printed zirconium oxide ceramic block blank for the all-ceramic false tooth, cleaning floating powder on the surface of the blank, and then carrying out cold isostatic pressing and reshaping after carrying out vacuum plastic package on the blank;
(10) placing the blank after cold isostatic pressing and reshaping into a box-type electric furnace, slowly heating for degreasing and presintering;
(11) according to the product specification requirements, the zirconium oxide ceramic block for the complete ceramic false tooth with the color and/or the light transmittance which are quasi-continuously changed along a determined direction is obtained after machining.
Furthermore, before ink-jet printing, according to the gradient requirement of quasi-continuous change of color and/or light transmittance, the descending stroke of the working platform or the thickness of the ink-jet printing layer is 5-500 μm, namely the thickness of the powder laying monolayer is 5-500 μm; the linear motor drives the powder box to spread powder along the horizontal direction and simultaneously uses a scraper to level the powder; before ink-jet printing, determining that the pixel of the two-dimensional section of the ink-jet printing of the permeation ink and/or the coloring ink and/or the blank ink is 0 multiplied by 0 to 2880 multiplied by 2880DPI and the repeated printing times PASS is 1 to 15 times according to the gradient requirement of quasi-continuous change of color and/or light transmittance.
Furthermore, according to the gradient requirement of quasi-continuous change of color and/or light transmittance, partially stabilized zirconia powder oxides containing yttrium oxide, cerium oxide, magnesium oxide, scandium oxide, samarium oxide, ytterbium oxide and/or calcium oxide with different types or contents are respectively or mixedly filled into one or more powder boxes, and the zirconia ceramic block blank for the all-ceramic false tooth with quasi-continuous change of color and light transmittance is obtained by controlling and changing the powder laying sequence of each powder box, the single descending stroke of the working platform, the powder laying thickness of each layer and the ink jet printing parameters of each layer of permeation ink and/or coloring ink and/or blank ink.
Furthermore, the zirconium oxide ceramic block blank for the all-ceramic false tooth taken out after the ink-jet printing is finished needs to be subjected to cold isostatic pressing of 50-350 MPa for reshaping, the relative density of the zirconium oxide ceramic block blank for the all-ceramic false tooth subjected to the cold isostatic pressing reshaping is larger than 50%, and then the zirconium oxide ceramic block blank for the all-ceramic false tooth is placed into a box-type furnace for degreasing at 200-650 ℃ and presintering at 850-1350 ℃. Finally, according to the product specification requirements, the zirconium oxide ceramic block for the full-ceramic false tooth with the color (color saturation) and/or the light transmittance quasi-continuous change along a determined direction is obtained after machining.
Example 1
By using a main body3 mol% Y having particle sizes of 1 to 10 μm, 10 to 50 μm and 50 to 100 μm2O3Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 5, 22 and 73 vol% to prepare special mixed powder for ink-jet printing with multistage distribution of particle size, and filling the special mixed powder into a No. 1 powder box; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; containing 17700ppmY3+And 50ppmAl3+The ionic aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink-jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total thickness to be 16.4mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of light transmittance and in consideration of the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out in monolayers of 200 μm thick (i.e. 82 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation. Determining blank ink jet printing parameters as follows: the initial pixel of the two-dimensional printing section is 100 multiplied by 100DPI, the front 2 layers adopt blank ink and are printed according to the pixel 100 multiplied by 100DPI (the number of ink-jet dots distributed on the two-dimensional printing section per inch), and the PASS number is 3 times; determining the inkjet printing parameters of the anti-reflection ink as follows: the 3 rd layer starts the two-dimensional printing section with 105 × 105DPI pixels, then each layer of pixels is added with 5 × 5DPI pixels until the final two-dimensional printing section with 500 × 500DPI printing pixels; the PASS numbers (number of repeated prints of a single layer) were all 9 times.
Starting a printing program, firstly, lowering the working platform by 200 microns, and driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by using a linear motor and leveling the powder by using a scraper; then the No. 0 ink gun prints according to the two-dimensional printing section pattern of the zirconia ceramic block blank (with the diameter of 132mm), blank ink is sprayed out from the nozzle of the No. 0 ink gun and the printing is repeated for 3 times, so that the powder layer with the thickness of 200 mu m is solidified; after completing the ink-jet printing of the layer, the working platform descends 200 microns again, the powder box moves to spread the powder again, then the 0# ink-jet head performs the ink-jet printing again and performs the printing 3 times, after 5 layers are printed in sequence, the working platform descends 200 microns continuously, the powder box moves to spread the powder again, the layer-by-layer ink-jet printing of the anti-reflection ink is performed by the 1# ink-jet head, and the printing is performed 3 times repeatedly, and every time when the thickness of the layer is 200 micronsAfter the thick powder layer is solidified, the working platform descends 200 microns again, the powder box moves to spread the powder again, then the No. 1 ink gun prints again and prints 3 times repeatedly, and the printing steps are repeated continuously until 82 layers (16.4mm thick) of the whole zirconia ceramic block blank are printed; cleaning floating powder on the surface of the zirconia ceramic block body, and increasing the average density of the zirconia ceramic block body to 3.06g/cm through 200MPa cold isostatic pressing3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, pre-sintering at 980 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, and pre-sintering until the average density of the zirconia ceramic block reaches 3.15g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the standard light transmittance quasi-continuous change of 98mm +/-0.5 mm in diameter and 12mm +/-0.5 mm in thickness is obtained through machining. The final densification sintering shows that the zirconia ceramic block for the full-ceramic false tooth is uniform white, the light transmittance gradient change of 10-49 percent is realized in the thickness direction, and the average bending strength is more than 980 MPa.
Example 2
4 mol% Y with particle sizes of 1-10 μm, 10-50 μm and 100-200 μm is adopted2O3Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 10, 25 and 65 vol% to prepare special mixed powder for ink-jet printing with multistage distribution of particle size, and filling the special mixed powder into a No. 1 powder box; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; 3192ppmFe3+、9.3ppmMn3+And 25047ppmEr3+The ionic aqueous solution coloring ink was loaded into the ink cartridge of the # 1 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total thickness to be 16.5mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color (color saturation) and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid down a monolayer thick of 500 μm (i.e. 33 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation. Determining blank ink jet printing parameters as follows: the starting pixel of the two-dimensional printing section is 100 multiplied by 100DPI, and the front 2 layers are adoptedPrinting with blank ink by 100 × 100DPI pixels for 5 times; determining the inkjet printing parameters of the pigmented ink as: the pixel of the starting two-dimensional printing cross section of the 3 rd layer is 40 × 40DPI, then 10 × 10DPI is added to each layer of pixels until the final printing pixel is 350 × 350 DPI; PASS number was 5.
Starting a printing program, firstly, lowering a working platform by 500 microns, driving a No. 1 powder box to lay powder on the working platform along the horizontal direction by a linear motor, and leveling the powder by a scraper; then the No. 0 ink-jet head prints according to the two-dimensional printing section pattern of the zirconia ceramic block blank (with the diameter of 132mm), and the nozzle of the No. 0 ink-jet head ejects white ink to solidify the powder layer with the thickness of 500 mu m and repeatedly prints for 5 times; after completing the ink-jet printing of the layer, the working platform descends by 500 microns again, the powder box moves to spread powder again, then the 0# ink-jet head performs ink-jet printing again and repeats printing for 5 times, after 2 layers are printed in sequence, the working platform descends by 500 microns continuously, the powder box moves to spread powder again, and starts to perform layer-by-layer ink-jet printing of the coloring ink by adopting the 1# ink-jet head and repeats printing for 5 times, after the powder layer with the thickness of 500 microns is solidified, the working platform descends by 500 microns again, the powder box moves to spread powder again, then the 1# ink-jet head prints again and repeats printing for 5 times, and the printing steps are repeated continuously until the printing of the whole zirconia ceramic block blank with 33 layers (16.5mm thick) is completed; cleaning floating powder on the surface of the zirconia ceramic block body, and performing 220MPa cold isostatic pressing to ensure that the average density of the zirconia ceramic block body reaches 3.08g/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, pre-sintering at 980 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, and pre-sintering the zirconia ceramic block with the average density of 3.14g/cm3(ii) a Finally, the zirconia ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 12mm +/-0.5 mm and the standard of quasi-continuous color change is obtained through machining. The final densification and sintering show that the zirconia ceramic block for the full-ceramic false tooth has the gradual change color of the color saturation from light to deep corresponding to the color of VITA 26 or VITA3D-Master color board 2M2 or VITA16 color comparison board A2 in the thickness direction and the uniform light transmittance of 40 percent, and the average bending strength is more than 1020 MPa.
Example 3
Using 3 mol% Y with particle sizes of 0.01-0.1 μm, 1-10 μm and 10-50 μm2O3Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 7, 19 and 74 vol% to prepare special ink-jet mixed powder with multistage distribution of particle size, and filling the special ink-jet mixed powder into a No. 1 powder box; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; will contain 1.32% Y2O3、0.02％MgO、0.01％CaO、0.005％TiO2And 0.005% Al2O3Filling the aqueous suspension anti-reflection ink of the nano mixed powder into an ink box of a No. 1 ink gun; 11350.3ppmFe3+、22.8ppmMn3+And 18828ppmEr3+The ionic aqueous solution coloring ink was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 25mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thick at 100 μm (i.e. 250 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining blank ink jet printing parameters as follows: the initial pixel of the two-dimensional printing section is 100 multiplied by 100DPI, the front 10 layers adopt blank ink and are printed according to the pixel 100 multiplied by 100DPI, and the PASS number is 2 times; determining the inkjet printing parameters of the pigmented ink as: the pixels of the two-dimensional printing section are always kept at 500 × 500DPI, and the PASS number is 1; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional print section is 1000 × 1000DPI and 20 × 20DPI is reduced every 3 layers until the final print pixel is 200 × 200 DPI; PASS number was 4. And from the 11 th layer, simultaneously printing layer by layer or alternately by using the 1# and 2# ink gun according to the ink-jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, descending the working platform by 100 microns, driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by the linear motor, and leveling the powder by a scraper; then the No. 0 ink-jet head prints according to the two-dimensional printing section pattern of the zirconia ceramic block green body (diameter 132mm)Ejecting blank ink from the nozzle of the 0# ink-jet head and continuously printing for 2 times to solidify a powder layer with the thickness of 100 μm; after the layer of ink-jet printing is finished, the working platform descends by 100 microns again, the powder box moves to spread powder again, then the 0# ink-jet head performs ink-jet printing again and continuously prints for 2 times, 10 layers of ink are sequentially printed, the working platform descends by 100 microns continuously, the powder box moves to spread powder again, then the 1# ink-jet head and the 2# ink-jet head perform simultaneous or alternate printing according to the two-dimensional printing cross-section graph of the zirconia ceramic block blank (with the diameter of 132mm), coloring ink is ejected from the nozzle of the 1# ink-jet head and is printed for 1 time, anti-reflection ink is ejected from the nozzle of the 2# ink-jet head and is printed for 2 times, and a powder layer with the thickness of 100 microns is solidified; after the layer of ink-jet printing is finished, the working platform descends by 100 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head perform ink-jet printing simultaneously or alternately again, and the printing steps are repeated continuously until the printing of 250 layers (25mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out 320MPa cold isostatic pressing to ensure that the average density of the zirconia ceramic block body is 3.12/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, pre-sintering at 980 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, and pre-sintering the zirconia ceramic block with the average density of 3.15g/cm3(ii) a Finally, the zirconia ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 18mm +/-0.5 mm and the standard color and light transmittance which are quasi-continuously changed is obtained by machining. The final densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has 40-10% of light transmittance gradient in the thickness direction and uniform color saturation corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 3M2 or VITA16 colorimetric plate A3, and the average bending strength is more than 850 MPa.
Example 4
Adopting 5.24 mol% Y with particle sizes of 0.01-0.1 μm, 1-10 μm and 10-50 μm2O3Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 7, 20 and 73 vol% to prepare special ink-jet mixed powder with particle sizes distributed in multiple stages, and filling the special ink-jet mixed powder into a No. 1 powder box; will have no effect onFilling blank ink of metal ions and nano metal oxide powder into an ink box of a 0# ink gun; 0.78 wt.% Fe2O3、0.00004wt.％MnO2And 1.04 wt.% Er2O3The aqueous suspension coloring ink of (1) was charged into the ink cartridge of the # 1 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 25mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thick of 100 μm (i.e. 250 layers in total were printed in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining blank ink jet printing parameters as follows: the initial pixel of the two-dimensional printing section is 100 multiplied by 100DPI, the front 10 layers adopt blank ink and are printed according to the pixel 100 multiplied by 100DPI, and the PASS number is 2 times; determining the inkjet printing parameters of the pigmented ink as: the starting pixel of the two-dimensional print cross-section is 500 × 500DPI and the 20 × 20DPI is reduced every 3 layers until the final print pixel is 200 × 200 DPI; PASS number was 2. Starting from layer 11, the layer-by-layer printing was performed using # 1 inkjet head according to the inkjet printing parameters of the pigmented ink.
Starting a printing program, firstly, descending the working platform by 100 microns, driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by the linear motor, and leveling the powder by a scraper; then the No. 0 ink gun prints according to the two-dimensional printing cross-sectional graph of the zirconia ceramic block blank (with the diameter of 132mm), blank ink is jetted out from the nozzle of the No. 0 ink gun and continuously prints for 2 times, and a powder layer with the thickness of 100 mu m is solidified; after the layer of ink-jet printing is finished, the working platform descends by 100 microns again, the powder box moves to spread powder again, then the 0# ink-jet head performs ink-jet printing again and continuously prints for 2 times, 10 layers of ink are printed in sequence, the working platform descends by 100 microns continuously, the powder box moves to spread powder again, then the 1# ink-jet head prints according to the two-dimensional printing cross-section graph of the zirconia ceramic block blank (with the diameter of 132mm), and the coloring ink is jetted out from the nozzle of the 1# ink-jet head and printed for 2 times, so that the powder layer with the thickness of 100 microns is solidified; after the layer of ink-jet printing is finished, the working platform descends by 100 microns again, the powder box moves again to spread the powder, and then the No. 1 ink-jet head performs ink-jet printing againContinuously repeating the printing steps until the printing of the whole zirconia ceramic block blank with 250 layers (thickness of 25 mm) is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out 320MPa cold isostatic pressing to ensure that the average density of the zirconia ceramic block body is 3.12/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, pre-sintering at 980 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, and pre-sintering the zirconia ceramic block with the average density of 3.15g/cm3(ii) a Finally, the zirconia ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 18mm +/-0.5 mm and the standard of quasi-continuous color change is obtained through machining. The final densification sintering shows that the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous color change has a gradual change color with the color saturation from light to deep and uniform light transmittance of 45 percent corresponding to the color of VITA 26 or VITA3D-Master color comparison plate 3M2 or VITA16 color comparison plate A3 in the thickness direction, and the average bending strength is more than 950 MPa.
Example 5
Using 3 mol% Y with particle sizes of 0.01-0.1 μm, 1-10 μm and 10-50 μm2O3Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 7, 19 and 74 vol% to prepare special ink-jet mixed powder with multistage distribution of particle size, and filling the special ink-jet mixed powder into a No. 1 powder box; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; will contain 44800ppmY3+、350ppmCe4+、220ppmMg2+、120ppmCa2+、50ppmTi4+And 100ppmAl3+The ion aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink gun; mixing 3252ppmFe3+、10.3ppmMn3+And 26500ppm Er3+The ionic aqueous solution coloring ink was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 25mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thick of 100 μm (i.e. 250 layers in total were printed in the thickness direction). At the same time, the product is formed by computer analysis and calculationThe two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132 mm; determining blank ink jet printing parameters as follows: the initial pixel of the two-dimensional printing section is 100 multiplied by 100DPI, the front 10 layers adopt blank ink and are printed according to the pixel 100 multiplied by 100DPI, and the PASS number is 2 times; determining the inkjet printing parameters of the pigmented ink as: the starting pixel of the two-dimensional print cross-section is 100 × 100DPI and 10 × 10DPI is added every 3 layers until the final print pixel is 900 × 900 DPI; PASS number 1; the inkjet printing parameters of the anti-reflection ink are as follows: the pixels of the two-dimensional printing section are always kept at 500 × 500DPI, and the PASS number is 4 times. And from the 11 th layer, simultaneously printing layer by layer or alternately by using the 1# and 2# ink gun according to the ink-jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, descending the working platform by 100 microns, driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by the linear motor, and leveling the powder by a scraper; then the No. 0 ink gun prints according to the two-dimensional printing cross-sectional graph of the zirconia ceramic block blank (with the diameter of 132mm), blank ink is jetted out from the nozzle of the No. 0 ink gun and continuously prints for 2 times, and a powder layer with the thickness of 100 mu m is solidified; after the layer of ink-jet printing is finished, the working platform descends by 100 microns again, the powder box moves to spread powder again, then the 0# ink-jet head performs ink-jet printing again and continuously prints for 2 times, 10 layers of ink are sequentially printed, the working platform descends by 100 microns continuously, the powder box moves to spread powder again, then the 1# ink-jet head and the 2# ink-jet head perform simultaneous or alternate printing according to the two-dimensional printing cross-section graph of the zirconia ceramic block blank (with the diameter of 132mm), coloring ink is ejected from the nozzle of the 1# ink-jet head and is printed for 1 time, anti-reflection ink is ejected from the nozzle of the 2# ink-jet head and is printed for 2 times, and a powder layer with the thickness of 100 microns is solidified; after the layer of ink-jet printing is finished, the working platform descends by 100 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head perform ink-jet printing simultaneously or alternately again, and the printing steps are repeated continuously until the printing of 250 layers (25mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out 320MPa cold isostatic pressing to ensure that the average density of the zirconia ceramic block body is 3.12/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating at a heating speed of less than 0.5 ℃/min,keeping the temperature at 350 ℃ for 5 hours for degreasing, keeping the temperature at 980 ℃ for presintering for 2 hours, then reducing the temperature at a speed of less than 0.5 ℃/min, and enabling the average density of the presintered zirconia ceramic block to be 3.15g/cm3(ii) a Finally, the zirconia ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 18mm +/-0.5 mm and the standard color and light transmittance which are quasi-continuously changed is obtained by machining. The final densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has uniform light transmittance of 45 percent and gradual change of color saturation from light to deep corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 2R1.5 or VITA16 colorimetric plate A2 in the thickness direction, and the average bending strength is larger than 960 MPa.
Example 6
Using 3.5 mol% Y with particle sizes of 0.01-0.1 μm, 1-10 μm and 10-50 μm2O3Mixing the partially stabilized zirconia powder according to the volume ratio of 4, 21 and 75 vol% to prepare special ink-jet mixed powder with particle sizes distributed in multiple stages, and filling the special ink-jet mixed powder into a No. 1 powder box; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; will contain 27000ppmY3+、50ppmTi4+And 100ppmAl3+The ion aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink gun; adding 11.4ppmMn3+、3141ppmFe3+And 6138ppmEr3+The ionic aqueous solution coloring ink was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 25mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thick of 100 μm (i.e. 250 layers in total were printed in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining blank ink jet printing parameters as follows: the initial pixel of the two-dimensional printing section is 100 multiplied by 100DPI, the front 10 layers adopt blank ink and are printed according to the pixel 100 multiplied by 100DPI, and the PASS number is 2 times; determining the inkjet printing parameters of the pigmented ink as: the starting pixel of the two-dimensional print cross-section is 200 x 200DPI, and 10 x 10DPI is added per 3 layers,until the final printed pixel is 1000 × 1000 DPI; PASS number 1; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional print section is 1000 × 1000DPI and 10 × 10DPI is reduced every 3 layers until the final print pixel is 200 × 200 DPI; PASS number was 4. And from the 11 th layer, simultaneously printing layer by layer or alternately by using the 1# and 2# ink gun according to the ink-jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, descending the working platform by 100 microns, driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by the linear motor, and leveling the powder by a scraper; then the No. 0 ink gun prints according to the two-dimensional printing cross-sectional graph of the zirconia ceramic block blank (with the diameter of 132mm), blank ink is jetted out from the nozzle of the No. 0 ink gun and continuously prints for 2 times, and a powder layer with the thickness of 100 mu m is solidified; after the layer of ink-jet printing is finished, the working platform descends by 100 microns again, the powder box moves to spread powder again, then the 0# ink-jet head performs ink-jet printing again and continuously prints for 2 times, 10 layers of ink are sequentially printed, the working platform descends by 100 microns continuously, the powder box moves to spread powder again, then the 1# ink-jet head and the 2# ink-jet head perform simultaneous or alternate printing according to the two-dimensional printing cross-section graph of the zirconia ceramic block blank (with the diameter of 132mm), coloring ink is ejected from the nozzle of the 1# ink-jet head and is printed for 1 time, anti-reflection ink is ejected from the nozzle of the 2# ink-jet head and is printed for 2 times, and a powder layer with the thickness of 100 microns is solidified; after the layer of ink-jet printing is finished, the working platform descends by 100 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head perform ink-jet printing simultaneously or alternately again, and the printing steps are repeated continuously until the printing of 250 layers (25mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out 320MPa cold isostatic pressing to ensure that the average density of the zirconia ceramic block body is 3.12/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, pre-sintering at 980 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, and pre-sintering the zirconia ceramic block with the average density of 3.15g/cm3(ii) a Finally, the zirconia ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 18mm +/-0.5 mm and the standard color and light transmittance which are quasi-continuously changed is obtained by machining. Through the process, finally, theThe densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has a light transmittance gradient of 45-10 percent in the thickness direction and a gradual change color of color saturation from light to deep corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 2L1.5 or VITA16 colorimetric plate B2, and the average bending strength is larger than 850 MPa.
Example 7
Using 3 mol% Y having particle sizes of 10 to 50 μm, 50 to 100 μm and 100 to 200 μm2O3Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 9, 23 and 68 vol% to prepare special mixed powder for ink-jet printing with multistage distribution of particle size, and filling the special mixed powder into a No. 1 powder box; 12700ppmY3+、150ppmCe4+、120ppmCa2+And 100ppmAl3+The ion aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink gun; 2.3 wt.% Fe2O3、0.0075wt.％MnO2And 14.6 wt.% Er2O3The aqueous suspension coloring ink of (2) was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 16.5mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thick of 500 μm (i.e. 33 layers in total were printed in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining the inkjet printing parameters of the pigmented ink as: the starting pixels (number of ink-jet dots distributed on each inch of the two-dimensional printing section) of the two-dimensional printing section are 10 × 10DPI, and 30 × 30DPI is added layer by layer until the final printing pixels are 1000 × 1000 DPI; PASS number (number of single-layer repeated printing) was 1; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional printing cross section is 1000 × 1000DPI, and 30 × 30DPI is reduced layer by layer until the final printing pixel is 10 × 10 DPI; PASS number was 9. And (3) printing layer by adopting the 1# ink gun and the 2# ink gun according to the ink-jet printing parameters of the color ink and the anti-reflection ink.
The printing program was started, first the work platform was lowered 500 μm, the linear motor beltSpreading powder on the working platform along the horizontal direction of the movable No. 1 powder box, and leveling the powder by using a scraper; then, the No. 1 ink gun and the No. 2 ink gun are simultaneously or alternately printed according to the two-dimensional printing section graph of the zirconia ceramic block blank (with the diameter of 132mm), coloring ink is jetted out from the nozzle of the No. 1 ink gun and is printed for 1 time, anti-reflection ink is jetted out from the nozzle of the No. 2 ink gun and is printed for 2 times, and the powder layer with the thickness of 500 microns is solidified; after the layer of ink-jet printing is finished, the working platform descends by 500 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head perform ink-jet printing simultaneously or alternately again, and the printing steps are repeated continuously until the printing of 33 layers (16.5mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 250MPa to ensure that the average density of the zirconia ceramic block body is 3.12g/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, pre-sintering at 980 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, and pre-sintering the zirconia ceramic block with the average density of 3.16g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 12mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has a light transmittance gradient of 46-10% in the thickness direction and a gradual change color of color saturation from light to deep corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 2R2.5 or VITA16 colorimetric plate A2, and the average bending strength is larger than 880 MPa.
Example 8
3 mol% Y with particle sizes of 1-10 μm, 10-50 μm and 50-100 μm respectively2O3Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 8, 22 and 70 vol% to prepare special mixed powder for ink-jet printing with multistage distribution of particle size, and filling the special mixed powder into a No. 1 powder box; will contain 42000ppmY3+、40ppmCe4+、50ppmMg2+、30ppmCa2+、12ppmTi4+And 25ppmAl3+The ion aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink gun; 1863.2ppm Fe3 +、5.44ppmMn3+And 14620ppmEr3+The ionic aqueous solution coloring ink was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 34m according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was applied in a monolayer thickness of 200 μm (i.e. 170 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining the inkjet printing parameters of the pigmented ink as: the starting pixels of the two-dimensional printing cross section (number of ink-jet dots distributed per inch of the two-dimensional printing cross section) are 1800 × 1800DPI, and 10DPI is reduced for each layer until the final printing pixels are 20 × 20 DPI; PASS number (number of single-layer repeated printing) was 1; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional print cross-section is 0 × 0DPI and 10 × 10DPI is added per 2 layers until the final print pixel is 840 × 840 DPI; PASS number was 4. And (3) simultaneously or alternately printing layer by adopting the 1# and 2# ink jet heads according to the ink jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, lowering the working platform by 200 microns, and driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by using a linear motor and leveling the powder by using a scraper; then, the No. 1 ink gun and the No. 2 ink gun are simultaneously or alternately printed according to the two-dimensional printing section graph of the zirconia ceramic block blank (with the diameter of 132mm), coloring ink is jetted out of a nozzle of the No. 1 ink gun, anti-reflection ink is jetted out of a nozzle of the No. 2 ink gun, and a powder layer with the thickness of 200 microns is solidified; after the ink-jet printing of the layer is finished, the working platform descends by 200 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head perform ink-jet printing simultaneously or alternately again, and the printing steps are repeated continuously until the printing of 170 layers (34mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 300MPa to ensure that the average density of the zirconia ceramic block body is 3.08g/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating at a heating rate of less than 0.5 ℃/min, preserving the temperature at 350 ℃ for 5 hours for degreasing, preserving the temperature at 980 ℃ for 2 hours for pre-sintering, and then carrying out pre-sinteringThe post-cooling speed is less than 0.5 ℃/min, and the average density of the pre-sintered zirconia ceramic block is 3.16g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 25mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has a light transmittance gradient of 12-48 percent in the thickness direction and a color saturation gradually changed from deep to light corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 2M2 or VITA16 colorimetric plate A2, and the average bending strength is larger than 980 MPa.
Example 9
5 mol% of CeO with the particle sizes of 1-10 mu m, 10-50 mu m and 50-100 mu m respectively2Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 7, 21 and 72 vol% to prepare special mixed powder for ink-jet printing with multistage distribution of particle size, and filling the special mixed powder into a No. 1 powder box; will contain 12300ppmY3+、50ppmTi4+And 100ppmAl3+The ion aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink gun; 464ppm of Fe3+、1.36ppm Mn3+And 3641.3ppm Er3+The ionic aqueous solution coloring ink was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 25mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thickness of 200 μm (i.e. 125 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining the inkjet printing parameters of the pigmented ink as: the starting pixels (number of ink-jet dots distributed on each inch of the two-dimensional printing section) of the two-dimensional printing section are 2880 × 2880DPI, and 20 × 20DPI is reduced layer by layer until the final printing pixels are 380 × 380 DPI; PASS number (number of repeated single-layer prints) was 2; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional print cross-section is 0 × 0DPI and 10 × 10DPI is added every 2 layers until the final print pixel is 620 × 620 DPI; PASS number was 9. Using 1# and 2# ink-jet heads simultaneouslyAnd simultaneously or alternately printing layer by layer according to the ink jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, lowering the working platform by 200 microns, and driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by using a linear motor and leveling the powder by using a scraper; then, the No. 1 ink gun and the No. 2 ink gun are simultaneously or alternately printed according to the two-dimensional printing section graph of the zirconia ceramic block blank (with the diameter of 132mm), coloring ink is jetted out from the nozzle of the No. 1 ink gun and is printed for 2 times, anti-reflection ink is jetted out from the nozzle of the No. 2 ink gun and is printed for 2 times, and the powder layer with the thickness of 200 microns is solidified; after the layer of ink-jet printing is finished, the working platform descends by 200 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head perform ink-jet printing simultaneously or alternately again, and the printing steps are repeated continuously until the printing of 125 layers (25mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 350MPa to ensure that the average density of the zirconia ceramic block body is 3.15g/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, and presintering at 990 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, wherein the average density of the presintered zirconia ceramic block is 3.18g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 18mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has a light transmittance gradient of 5-40 percent in the thickness direction and a color saturation gradually changed from deep to light corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 2R1.5 or VITA16 colorimetric plate A2, and the average bending strength is larger than 945 MPa.
Example 10
8 mol% MgO partially stabilized zirconia spherical powder with the particle sizes of 1-10 mu m, 10-50 mu m and 50-100 mu m is mixed according to the volume proportion of 8, 22 and 70 vol% to prepare special mixed powder for ink-jet printing with the particle sizes distributed in multiple stages, and the special mixed powder is filled into a No. 1 powder box; will contain 39850ppmY3+、450ppmCe4+And 20ppmTi4+Of ionsThe anti-reflection ink of the aqueous solution is filled into an ink box of a No. 1 ink gun; 931.6ppm Fe3+、2.72ppmMn3+And 7310ppmEr3+The ionic aqueous solution coloring ink was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 34mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out in monolayers of 200 μm thick (i.e. 170 layers in total were printed in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining the inkjet printing parameters of the pigmented ink as: the starting pixels (number of ink-jet dots distributed per inch of the two-dimensional printing section) of the two-dimensional printing section are 1800 × 1800DPI, and 10 × 10DPI is reduced layer by layer until the final printing pixels are 20 × 20 DPI; PASS number (number of repeated single-layer prints) was 2; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional print cross-section is 0 × 0DPI and 10 × 10DPI is added per 2 layers until the final print pixel is 840 × 840 DPI; PASS number was 4. And respectively, simultaneously or alternately printing layer by adopting the 1# ink gun and the 2# ink gun according to the ink-jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, lowering the working platform by 200 microns, and driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by using a linear motor and leveling the powder by using a scraper; then, the 1# ink gun and the 2# ink gun respectively or simultaneously or alternatively print according to the two-dimensional printing cross section pattern of the zirconia ceramic block blank (with the diameter of 132mm), the colored ink is ejected from the nozzle of the 1# ink gun and the anti-reflection ink is ejected from the nozzle of the 2# ink gun, and the 1# ink gun and the 2# ink gun respectively or simultaneously or alternatively print for 2 times to solidify the powder layer with the thickness of 200 microns; after the ink-jet printing of the layer is finished, the working platform descends by 200 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head respectively or simultaneously or alternatively perform ink-jet printing again, and the printing steps are continuously repeated until the printing of 170 layers (34mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 300MPa to enable the average density of the zirconia ceramic block body to reach3.08g/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, pre-sintering at 980 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, and pre-sintering until the average density of the zirconia ceramic block reaches 3.16g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 25mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has a light transmittance gradient of 12-45 percent in the thickness direction, the color saturation corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 2M2 or VITA16 colorimetric plate A2 is continuously changed from deep to light, and the average bending strength is more than 950 MPa.
Example 11
Mixing 6 mol% CaO partially stabilized zirconia spherical powder with the particle sizes of 1-10 mu m, 10-50 mu m and 50-100 mu m according to the volume proportion of 8, 22 and 70 vol% to prepare special mixed powder for ink-jet printing with the particle sizes distributed in multiple stages, and filling the special mixed powder into a No. 1 powder box; will contain 8700ppmY3+、40ppmCe4+、20ppmMg2+、300ppmCa2+And 50ppmTi4+The ion aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink gun; 1.0 wt.% Fe2O3、0.0033wt.％MnO2And 6.5 wt.% Er2O3The aqueous suspension coloring ink of (2) was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 34mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out in monolayers of 200 μm thick (i.e. 170 layers in total were printed in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining the inkjet printing parameters of the pigmented ink as: the starting pixel of the two-dimensional printing cross section is 1000 × 1000DPI, and the 5 × 5DPI is reduced layer by layer until the final printing pixel is 150 × 150 DPI; PASS number 1; the inkjet printing parameters of the anti-reflection ink are: the starting pixel of the two-dimensional print cross-section is 0 × 0DPI and 10DPI is added per 2 layers until the final print pixel is 840 × 840 DPI; PASS number was 9. And simultaneously or alternately printing layer by adopting the 1# ink gun and the 2# ink gun according to the ink-jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, lowering the working platform by 200 microns, and driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by using a linear motor and leveling the powder by using a scraper; then, the 1# ink gun and the 2# ink gun respectively or simultaneously or alternatively print according to the two-dimensional printing cross section pattern of the zirconia ceramic block blank (with the diameter of 132mm), the colored ink is ejected from the nozzle of the 1# ink gun and the anti-reflection ink is ejected from the nozzle of the 2# ink gun, and the 1# ink gun and the 2# ink gun respectively or simultaneously or alternatively print for 1 time to solidify the powder layer with the thickness of 200 microns; after the layer of ink-jet printing is finished, the working platform descends by 200 microns again, the powder box moves to spread powder again, and then the 1# ink-jet head and the 2# ink-jet head respectively or simultaneously or alternatively perform ink-jet printing again; continuously repeating the printing steps until the printing of the whole zirconia ceramic block blank with 170 layers (34mm thick) is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 300MPa to ensure that the average density of the zirconia ceramic block body reaches 3.10g/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours for degreasing, pre-sintering at 1010 ℃ for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, and pre-sintering until the average density of the zirconia ceramic block reaches 3.18g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 25mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has a light transmittance gradient of 12-55% in the thickness direction and a color saturation gradually changed from deep to light corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 2M2 or VITA16 colorimetric plate A2, and the average bending strength is more than 1100 MPa.
Example 12
Using 3 mol% Y with particle sizes of 0.01-0.1 μm, 0.1-1 μm, and 1-10 μm2O3Partially stabilized oxygenMixing the zirconium oxide spherical powder according to the volume proportion of 8, 20 and 72 vol% to prepare special mixed powder for ink-jet printing, wherein the particle size of the special mixed powder is distributed in multiple stages, and filling the special mixed powder into a No. 1 powder box; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; will contain 4.64 wt.% Y2O3、0.05wt.％MgO、0.25wt.％CaO、0.01wt.％TiO2And 0.01 wt.% Al2O3Filling the anti-reflection ink of the aqueous suspension solution of the composite nano powder into an ink box of a No. 1 ink gun; 1562.4ppm Fe3+、5.7ppm Mn3+And 3068.9ppm Er3+The ionic aqueous solution coloring ink was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 16.4mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thickness of 50 μm (i.e. 328 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining the inkjet printing parameters of the pigmented ink as: the starting pixel of the two-dimensional print section is 180 × 180DPI and 5 × 5DPI is added every 2 layers until the final print pixel is 1000 × 1000 DPI; PASS number 1; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional print cross-section is 1000 × 1000DPI and 10 × 10DPI is reduced every 4 layers until the final print pixel is 190 × 190 DPI; PASS number was 4. And (3) simultaneously or alternately printing layer by adopting the 1# and 2# ink jet heads according to the ink jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, lowering the working platform by 50 microns, and driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by using a linear motor and leveling the powder by using a scraper; then, the 1# ink gun and the 2# ink gun respectively or simultaneously or alternatively print according to the two-dimensional printing cross section pattern of the zirconia ceramic block blank (with the diameter of 132mm), coloring ink is ejected from a nozzle of the 1# ink gun, anti-reflection ink is ejected from a nozzle of the 2# ink gun, and the 1# ink gun and the 2# ink gun respectively or simultaneously or alternatively print to solidify a powder layer with the thickness of 50 microns; after the ink-jet printing of the layer is finished, the working platformThe platform descends by 50 microns again, the powder box moves to spread powder again, and then the 1# ink gun and the 2# ink gun respectively or simultaneously or alternatively jet-print again; continuously repeating the printing steps until the printing of the whole zirconia ceramic block blank with 328 layers (16.4mm thick) is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 350MPa to ensure that the average density of the zirconia ceramic block body is 3.10/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating at a heating rate of less than 0.5 ℃/min, keeping the temperature at 350 ℃ for 5 hours for degreasing, pre-sintering at 1020 ℃ for 2 hours, then cooling at a speed of less than 0.5 ℃/min, and pre-sintering the zirconia ceramic block with the average density of 3.12g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 12mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification and sintering show that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has 48-15% of light transmittance gradient and gradual change color of color saturation from light to deep corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 2L1.5 or 2L2.5 or VITA16 colorimetric plate B2, and the average bending strength is more than 1202 MPa.
Example 13
Taking Y containing 3 mol%, 4 mol%, 5 mol% and 6 mol% respectively2O3The 4 partially stabilized zirconia spherical powders of (1) are each in three specifications of 0.01 to 0.1 μm, 0.1 to 1 μm and 1 to 10 μm in terms of particle size. Mixing each powder according to three particle size specifications according to the volume proportion of 8, 20 and 72 vol% respectively to prepare 4 partially stabilized zirconia special mixed powder with particle sizes distributed in a multistage manner for ink-jet printing, and filling the powder into powder boxes 1#, 2#, 3# and 4# respectively; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; will contain 0.00080 wt.% Fe2O3、0.0000075wt.％MnO2、0.000008wt.％Co3O4And 0.222 wt.% Er2O3The aqueous coloring ink of the nano metal oxide powder is filled into the ink cartridge of the # 1 ink jet head. According to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with the quasi-continuous change of the color and/or the light transmittance, and in consideration of the requirementsConsidering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering, setting the diameter of the zirconia ceramic block blank to be 132mm and the total printing thickness to be 16.4 mm; the powder was laid out a monolayer thickness of 50 μm (i.e. 328 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining powder paving procedures of four special mixed powder for partially stabilized zirconia ink-jet printing, and sequentially replacing powder boxes 1#, 2#, 3# and 4# at intervals of 70 layers for powder paving; determining blank ink jet printing parameters as follows: the starting pixels of the two-dimensional printed section are: 120 × 120DPI, the PASS number is 1 time, the front 10 layers adopt blank ink and are printed according to the pixel 120 × 120 DPI; determining the inkjet printing parameters of the pigmented ink as: the starting pixel of the two-dimensional print cross-section is 160 × 160DPI and 10 × 10DPI is added per 2 layers until the final print pixel is 1800 × 1800 DPI; PASS number was 1. Starting from layer 11, the layer-by-layer printing was performed using # 1 inkjet head according to the inkjet printing parameters of the pigmented ink.
Starting a printing program, firstly, lowering the working platform by 50 microns, and driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by using a linear motor and leveling the powder by using a scraper; then the No. 0 ink gun prints according to the two-dimensional printing cross-section graph of the zirconia ceramic block blank (with the diameter of 132mm), blank ink is sprayed out of a nozzle of the No. 0 ink gun, and a powder layer with the thickness of 50 microns is solidified; after the ink-jet printing of the layer is finished, the working platform descends by 50 microns again, the powder box 1# moves to spread the powder again, then the ink-jet printing of the ink-jet head 0# is carried out again, 10 layers of printing are sequentially repeated, the working platform descends by 50 microns continuously, the powder box 1# moves to spread the powder again, then the ink-jet head 1# begins to print according to the two-dimensional printing section graph of the zirconium oxide ceramic block blank (with the diameter of 132mm), the coloring ink is ejected out of the nozzle of the ink-jet head 1# to enable the powder layer with the thickness of 50 microns to be solidified. When the powder spreading of the 83 th layer is started, spreading the powder on the working platform along the horizontal direction by the 2# powder box, and leveling the powder by a scraper; when the 164 th layer of powder spreading is started, spreading the powder on the working platform by the 3# powder box along the horizontal direction and leveling the powder by a scraper; when the 246 th layer of powder spreading is started, spreading the 4# powder box on the working platform along the horizontal direction, and leveling the powder by using a scraper; after each layer of powder is laid, the 1# ink gun prints the powder according to the ink jetPrinting is performed with a starting pixel of a two-dimensional print cross-section (a circular image of 132mm diameter) of 100 × 100DPI and 10DPI added per 2 layers until the final print pixel is 1800 × 1800 DPI; PASS number was 1. After each layer of powder (50 mu m thick) is printed by ink jet, the working platform descends by 50 mu m, the powder box moves to spread the powder again, then the No. 1 ink gun prints again, and the printing steps are repeated continuously until 328 layers (16.4mm thick) of the whole zirconia ceramic block blank are printed; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 300MPa to ensure that the average density of the zirconia ceramic block body is 3.12/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating at a heating rate of less than 0.5 ℃/min, preserving the heat at 500 ℃ for 5 hours for degreasing, preserving the heat at 980 ℃ for 2 hours for presintering, then cooling at a speed of less than 0.5 ℃/min, and presintering the zirconia ceramic block with the average density of 3.15g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 12mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification and sintering show that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has the light transmittance gradient change of 10-55% in the thickness direction and the quasi-continuous gradient of light-to-deep color saturation corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 3R1.5, 4R1.5 or VITA16 colorimetric plate D3, and the average bending strength is more than 1110 MPa.
Example 14
Taking 7 partially stabilized zirconia spherical powders respectively containing 3 mol%, 5 mol%, 7 mol%, 9 mol%, 11 mol%, 13 mol% and 15 mol% of CaO, wherein each powder is divided into three specifications of 0.01-0.1 μm, 0.1-1 μm and 1-10 μm according to different particle sizes. Mixing each powder according to three particle size specifications according to the volume proportion of 8, 20 and 72 vol% respectively to prepare 7 partially stabilized zirconia special mixed powder for ink-jet printing, wherein the particle sizes of the 7 partially stabilized zirconia special mixed powder are distributed in a multistage manner, and filling the 7 partially stabilized zirconia special mixed powder into powder boxes 1#, 2#, 3#, 4#, 5#, 6# and 7# respectively; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; will contain 1.4 wt.% Fe2O3、0.004wt.％MnO2And 8.7 wt.% Er2O3Nano goldThe photo-curable coloring ink, which is oxide powder, is charged into the ink cartridge of the # 1 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 16.8mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thick of 100 μm (i.e. 168 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing image with a cross section of 132mm in diameter is formed by computer analysis and calculation of the zirconia ceramic block blank; determining 7 powder paving procedures of the special mixed powder for partially stabilized zirconia ink-jet printing, and sequentially replacing powder boxes 1#, 2#, 3#, 4#, 5#, 6# and 7# for powder paving every 24 layers; determining blank ink jet printing parameters as follows: the initial pixel of the two-dimensional printing section is 120 multiplied by 120DPI, the front 8 layers adopt blank ink and are printed according to the pixel 120 multiplied by 120DPI, and the PASS number is 1 time; determining the inkjet printing parameters of the pigmented ink as: the pixels of the two-dimensional printing section are always kept at 100 × 100 DPI; the initial PASS number was 1, the PASS number was increased by 1 for each 20-layer printing completion, and the final PASS number was 8. Starting from layer 9, the layer by layer printing is carried out by using the 1# ink-jet head according to the ink-jet printing parameters of the colored ink.
Starting a printing program, firstly, descending the working platform by 100 microns, driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by the linear motor, and leveling the powder by a scraper; then the No. 0 ink gun prints according to the two-dimensional printing cross-section graph of the zirconia ceramic block blank (with the diameter of 132mm), blank ink is sprayed out of a nozzle of the No. 0 ink gun, and a powder layer with the thickness of 100 mu m is solidified; after the ink-jet printing of the layer is finished, the working platform descends by 100 microns again, the powder box 1# moves to spread the powder again, then the ink-jet printing of the ink-jet head 0# is carried out again, after 8 layers are printed in sequence, the working platform descends by 100 microns continuously, the powder box 1# moves to spread the powder again, then the ink-jet head 1# begins to print according to the two-dimensional printing cross-section graph of the zirconium oxide ceramic block blank (with the diameter of 132mm), and the coloring ink is jetted out from the nozzle of the ink-jet head 1# to solidify the powder layer with the thickness of 100 microns. When the 25 th layer of powder spreading is started, spreading the powder on the working platform along the horizontal direction by the 2# powder box, and leveling the powder by a scraper; when the 49 th layer of powder is paved, paving powder on the working platform by the 3# powder box along the horizontal direction, and leveling the powder by a scraper; when the 73 rd layer of powder spreading is started, spreading the 4# powder box on the working platform along the horizontal direction, and leveling the powder by using a scraper; when the 97 th layer of powder spreading is started, spreading the 5# powder box on the working platform along the horizontal direction, and leveling the powder by using a scraper; when the 121 st layer of powder spreading is started, spreading powder on the working platform along the horizontal direction by the 6# powder box, and leveling the powder by a scraper; when the 145 th layer of powder spreading was started, the 7# powder container was spread on the work platform in the horizontal direction while leveling the powder with a spatula. After powder spreading of each layer is finished, the 1# ink gun prints according to ink-jet printing parameters, and pixels of a two-dimensional printing section (a circular image with the diameter of 132mm) are always kept at 120 × 120 DPI; the initial PASS number is 1, and the PASS number increases by 1 for each 20 layers of printing completed, and finally the 140 th layer starts the PASS number by 8. Starting from layer 9, the layer by layer printing is carried out by using the 1# ink-jet head according to the ink-jet printing parameters of the colored ink.
After each layer of powder (100 mu m thick) is printed by ink-jet, the working platform descends by 100 mu m, the powder box moves to spread the powder again, then the No. 1 ink-jet head prints again, and the printing steps are repeated continuously until 168 layers (16.8mm thick) of the whole zirconia ceramic block blank are printed; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 300MPa to ensure that the average density of the zirconia ceramic block body is 3.08/cm3(ii) a Putting the zirconia ceramic block blank into a box-type electric furnace, slowly heating at a heating rate of less than 0.5 ℃/min, preserving the heat at 500 ℃ for 5 hours for degreasing and at 1000 ℃, presintering for 2 hours, then cooling at a speed of less than 0.5 ℃/min, and enabling the average density of the presintered zirconia ceramic block to be 3.12g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 12mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification and sintering show that the zirconium oxide porcelain blocks for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance have 5-65% light transmittance gradient change in the thickness direction and quasi-continuous gradual change of color saturation corresponding to VITA 26 or VITA3D-Master colorimetric plate 2M2, 2R1.5, 2R2.5 or VITA16 colorimetric plate A2, and the average bending strength is larger than 860 MPa.
Example 15
By the particle size of10 mol% Sc of 1 to 10 μm, 10 to 50 μm and 50 to 100 μm2O3Mixing the partially stabilized zirconia spherical powder according to the volume ratio of 7, 19 and 74 vol% to prepare special ink-jet mixed powder with multistage distribution of particle size, and filling the special ink-jet mixed powder into a No. 1 powder box; filling blank ink without metal ions and nano metal oxide powder into an ink box of a 0# ink gun; will contain 39800ppmY3+、220ppmMg2+、520ppmCa2+、150ppmTi4+And 100ppmAl3+The ion aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink gun; 0.26 wt.% Fe2O3、0.00084wt.％MnO2And/or 1.64 wt.% Er2O3The aqueous suspension of nano-metal oxide powder coloring ink was loaded into the cartridge of the # 2 ink-jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 25mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thickness of 200 μm (i.e. 125 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing section of the zirconia ceramic block blank is a circular image with the diameter of 132mm through computer analysis and calculation; determining blank ink jet printing parameters as follows: the starting pixel of the two-dimensional printing cross section is 100 × 100DPI, the first 10 layers are printed with blank ink and each is printed at 100 × 100DPI by pixels, and the PASS number is 1. Determining the inkjet printing parameters of the pigmented ink as: the starting pixel of the two-dimensional print cross-section is 75 × 75DPI and 15 × 15DPI is added per 1 layer until the final print pixel is 1800 × 1800 DPI; PASS number 1; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional print cross-section is 800 × 800DPI and 10 × 10DPI is reduced per 2 layers until the final print pixel is 225 × 225 DPI; PASS number was 4. And from the 11 th layer, respectively, simultaneously or alternately printing layer by using the 1# and 2# ink-jet heads according to the ink-jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, lowering the working platform by 200 microns, and driving the No. 1 powder box to lay powder on the working platform along the horizontal direction by using a linear motor and leveling the powder by using a scraper; then 0# ink jet head following the zirconia ceramic block blank (diameter 1)32mm), and spraying blank ink from a nozzle of a 0# ink-jet head to solidify a powder layer with the thickness of 200 microns; after the layer of ink-jet printing is finished, the working platform descends 200 microns again, the powder box moves to spread powder again, then the 0# ink-jet head performs ink-jet printing again, 10 layers of ink are sequentially printed, the working platform descends 200 microns continuously, the powder box moves to spread powder again, then the 1# ink-jet head and the 2# ink-jet head perform printing respectively, simultaneously or alternately according to the two-dimensional printing cross-sectional graph of the zirconia ceramic block blank (with the diameter of 132mm), coloring ink is jetted out from the nozzle of the 1# ink-jet head, anti-reflection ink is jetted out from the nozzle of the 2# ink-jet head, and the powder layer with the thickness of 200 microns is solidified; after the layer of ink-jet printing is finished, the working platform descends by 200 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head respectively or simultaneously or alternatively perform ink-jet printing again, and the printing steps are continuously repeated until the printing of 125 layers (25mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out cold isostatic pressing at 300MPa to ensure that the average density of the zirconia ceramic block body is 3.10/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating up at a heating rate of less than 0.5 ℃/min, keeping the temperature at 350 ℃ for 5 hours for degreasing, and at 995 ℃ for presintering for 2 hours, then cooling down at a speed of less than 0.5 ℃/min, wherein the average density of the presintered zirconia ceramic block is 3.16g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 18mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification sintering shows that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has 55-24% of light transmittance gradient in the thickness direction and quasi-continuous gradient of color saturation from light to deep corresponding to VITA 26 or VITA3D-Master colorimetric plate 2M2 color or VITA16 colorimetric plate A2 color, and the average bending strength is larger than 940 MPa.
Example 16
1 mol% Yb with particle sizes of 1-10 μm, 10-50 μm and 50-100 μm respectively2O3And 1 mol% of Y2O3The composite stabilizer partially stabilized zirconia spherical powder is mixed according to the volume proportion of 7, 19 and 74 vol% to prepare the particle size with multi-stage distributionThe special mixed powder for ink jet is filled into a No. 1 powder box; filling blank ink without metal ions and nano metal oxide powder into an ink box of a No. 0 ink-jet head; will contain 30700ppmY3+And 150ppmAl3+The ion aqueous solution anti-reflection ink is filled into an ink box of the No. 1 ink gun; 3.0 wt.% Fe2O3、0.028wt.％MnO2、0.000005wt.％Co3O4And 8.3 wt.% Er2O3The aqueous suspension coloring ink of (2) was charged into the ink cartridge of the # 2 ink jet head. Setting the diameter of a zirconia ceramic block blank to be 132mm and the total printing thickness to be 26mm according to the performance and specification requirements of the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and/or light transmittance and considering the shrinkage of the zirconia ceramic block blank after cold isostatic pressing and presintering; the powder was laid out a monolayer thick of 500 μm (i.e. 52 layers were printed in total in the thickness direction). Meanwhile, a two-dimensional printing image with a cross section of 132mm in diameter is formed by computer analysis and calculation of the zirconia ceramic block blank; determining blank ink jet printing parameters as follows: the starting pixel of the two-dimensional printing cross section is 100 × 100DPI, the first 2 layers are printed with blank ink and each pixel is 100 × 100DPI, and the PASS number is 1. Determining the inkjet printing parameters of the pigmented ink as: the starting pixel of the two-dimensional print section is 0 × 0DPI, and 20 × 20DPI is added every 1 layer until the final print pixel is 1000 × 1000 DPI; PASS number 1; the inkjet printing parameters of the anti-reflection ink are as follows: the starting pixel of the two-dimensional print cross-section is 600 × 600DPI and 10 × 10DPI is reduced every 1 layer until the final print pixel is 50 × 50 DPI; PASS number was 9. And from the 3 rd layer, simultaneously printing layer by layer or alternately by using the 1# and 2# ink jet heads according to the ink jet printing parameters of the color ink and the anti-reflection ink.
Starting a printing program, firstly, lowering a working platform by 500 microns, driving a No. 1 powder box to lay powder on the working platform along the horizontal direction by a linear motor, and leveling the powder by a scraper; then the No. 0 ink gun prints according to the two-dimensional printing section pattern of the zirconia ceramic block blank (with the diameter of 132mm), and white ink is jetted from a nozzle of the No. 0 ink gun to solidify a powder layer with the thickness of 500 mu m; after the layer of ink-jet printing is finished, the working platform descends by 500 microns again, the powder box moves to spread the powder again, then the 0# ink-jet head prints the ink again, and the ink-jet printing is carried out on the powder box again in sequenceAfter printing 2 layers, continuously descending the working platform by 500 microns, moving the powder box again to spread powder, then respectively or simultaneously or alternately printing the 1# ink-jet head and the 2# ink-jet head according to a two-dimensional printing cross-section graph of a zirconia ceramic block blank (with the diameter of 132mm), ejecting coloring ink from a nozzle of the 1# ink-jet head, and ejecting anti-reflection ink from a nozzle of the 2# ink-jet head to solidify a powder layer with the thickness of 500 microns; after the ink-jet printing of the layer is finished, the working platform descends by 500 microns again, the powder box moves to spread the powder again, then the 1# ink-jet head and the 2# ink-jet head respectively or simultaneously or alternatively perform ink-jet printing again, and the printing steps are continuously repeated until the printing of 52 layers (26mm thick) of the whole zirconia ceramic block blank is finished; cleaning floating powder on the surface of the zirconia ceramic block body, and then carrying out 320MPa cold isostatic pressing to ensure that the average density of the zirconia ceramic block body is 3.12/cm3(ii) a Putting the zirconia ceramic block body into a box-type electric furnace, slowly heating at a heating rate of less than 0.5 ℃/min, preserving the heat at 350 ℃ for 5 hours, degreasing at 970 ℃, presintering for 2 hours, then cooling at a speed of less than 0.5 ℃/min, and presintering the zirconia ceramic block with the average density of 3.12g/cm3(ii) a Finally, the zirconium oxide ceramic block for the full-ceramic false tooth with the diameter of 98mm +/-0.5 mm and the thickness of 18mm +/-0.5 mm and with the color and the light transmittance changing is obtained through machining. The final densification and sintering show that the zirconium oxide porcelain block for the full-porcelain false tooth with quasi-continuous change of color and/or light transmittance has 55-16% of light transmittance gradient in the thickness direction and quasi-continuous gradient of color saturation from light to deep corresponding to the color of VITA 26 or VITA3D-Master colorimetric plate 4R1.5 or VITA16 colorimetric plate D3, and the average bending strength is larger than 990 MPa.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may be modified or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (11)

1. The zirconia ceramic block for the all-ceramic false tooth is characterized in that partially stabilized zirconia powder is adopted as a raw material of the zirconia ceramic block for the all-ceramic false tooth, powder is periodically spread layer by layer along a determined direction, blank ink, coloring ink with different solute concentrations and anti-reflection ink with different solute concentrations are adopted, and ink-jet printing and overlapping are selectively performed layer by layer or simultaneously or alternately, wherein the color and the light transmittance of the zirconia ceramic block for the all-ceramic false tooth are quasi-continuously changed from one side to the other side along the determined direction;
the partially stabilized zirconia powder is prepared by mixing irregular particles and/or spherical particles with the sizes of 0.01-0.1 mu m, 0.1-1 mu m, 1-10 mu m, 10-50 mu m, 50-100 mu m and 100-200 mu m according to different proportions, the particle sizes are distributed in a multistage way, the irregular particles and/or the spherical particles are formed by combining nano crystal grains, and the crystal grain sizes are 5-200 nm;
the anti-reflection ink and the coloring ink contain nano oxide powder and/or metal ions, and also contain a water-based, non-water-based or photo-curing binder, a humectant, a quick drying agent, a lubricant, a coagulant, a flow increasing agent, a defoaming agent and a pH regulator, wherein the pH values of the anti-reflection ink and the coloring ink are both 5-9, and the viscosities of the anti-reflection ink and the coloring ink are both 1-500 mPa & s;
the blank ink does not contain any nano oxide powder and/or any metal ions, but contains a water-based, non-water-based or photo-curing binder, a humectant, a quick drying agent, a lubricant, a coagulant, a flow increasing agent, a defoaming agent and a pH regulator, and has a pH value of 5-9 and a viscosity of 1-500 mPa & s;
by using a catalyst containing CeO2、Fe2O3、Mn2O3、Pr2O3、Er2O3、TiO2、GeO2、ZrO2、Al2O3、CaO、CuO、Co3O4、NiO、V2O5、Cr2O3、In2O3、Dy2O3、Eu2O3、Ga2O3、Ho2O3、Tb2O3、RuO2、SnO2、Bi2O3And/or Tm2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders or containing Ce4+、Fe3+、Mn3+、Pr3+、Er3+、Ti4+、Ge4+、Zr4+、Al3+、Ca2+、Cu2+、Co2+、Co3+、Ni2+、V5+、Cr3+、In3+、Dy3+、Eu3+、Ga3+、Ho3+、Tb3+、Ru4+、Sn4+、Bi3+And/or Tm3+Ionic aqueous, non-aqueous or photocurable solutions as coloring inks; by using a compound containing Y2O3、La2O3、Sc2O3、Nd2O3、Yb2O3、Gd2O3、Sm2O3、Mn2O3、Er2O3、ThO2、TiO2、CeO2MgO, CaO and/or Al2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders or containing Y3+、La3+、Sc3+、Nd3+、Yb3+、Gd3+、Sm3+、Mn3+、Er3+、Th4+、Ti4+、Ce4+、Mg2+、Ca2+And/or Al3+The ionic water-based, non-water-based or light-cured solution is used as anti-reflection ink, and the particle size of nano metal oxide powder used by coloring ink and anti-reflection ink is less than 100 nm; the metal ions used in the coloring ink and the anti-reflection ink are selected from one or more of chloride, nitrate, carbonate, sulfate, acetate, glutarate, malate, gluconate, fumarate, oxalate, lactate and citrate.
2. The zirconia porcelain block for an all-ceramic denture as claimed in claim 1, wherein said determined direction is a thickness direction of the powder, which is perpendicular to the direction of powder application of each layer, and the color gradually changes from dark color to light color and the light transmittance gradually changes from 5% to 70% quasi-continuously from one side to the other side along the direction, and each layer of the powder has a thickness of 5 μm to 500 μm.
3. The zirconia ceramic block for an all-ceramic denture according to claim 1, wherein the partially stabilized zirconia powder optionally comprises an oxide as a stabilizer, wherein the oxide comprises one or more of yttria, ceria, magnesia, scandia, samaria, ytterbia or calcia.
4. The zirconia porcelain block for a full ceramic denture as claimed in claim 3, wherein the partially stabilized zirconia powder contains less than 30 mol% of total stabilizers, wherein the yttria content is 0 to 8 mol%, the ceria content is 0 to 30 mol%, the magnesia content is 0 to 15 mol%, the scandia content is 0 to 15 mol%, the samaria content is 0 to 15 mol%, the ytterbia content is 0 to 15 mol% and/or the calcia content is 0 to 18 mol%.
5. The zirconia ceramic block for a full ceramic denture as claimed in claim 1, wherein the colored ink contains CeO in the colored ink2、Fe2O3、Mn2O3、Pr2O3、Er2O3、TiO2、GeO2、ZrO2、Al2O3、CaO、CuO、Co3O4、NiO、V2O5、Cr2O3、In2O3、Dy2O3、Eu2O3、Ga2O3、Ho2O3、Tb2O3、RuO2、SnO2、Bi2O3And/or Tm2O3The content of the nano metal oxide powder is 0.000001 to 10 weight percent respectively or Ce in the colored ink4+、Fe3+、Mn3+、Pr3+、Er3+、Ti4+、Ge4+、Zr4+、Al3+、Ca2+、Cu2+、Co2+、Co3+、Ni2+、V5+、Cr3+、In3+、Dy3+、Eu3+、Ga3+、Ho3+、Tb3+、Ru4+、Sn4+、Bi3+And/or Tm3+The ion solubility is 5 to 100000 ppm.
6. The zirconia ceramic block for a full ceramic denture as claimed in claim 1, wherein Y in the penetration-enhancing ink2O3、La2O3、Sc2O3、Nd2O3、Yb2O3、Gd2O3、Sm2O3、Mn2O3、Er2O3、ThO2、TiO2、CeO2MgO, CaO and/or Al2O3The content of the nano metal oxide powder is 0.000001 wt% -10 wt% respectively; or Y in antireflective inks3+、La3+、Sc3+、Nd3+、Yb3+、Gd3+、Sm3+、Mn3+、Er3+、Th4+、Ti4+、Ce4+、Mg2+、Ca2+And/or Al3+The ion solubility is 5 to 100000 ppm.
7. The process for preparing the zirconia ceramic block for the all-ceramic denture according to any one of claims 1 to 6, wherein partially stabilized zirconia powder is used as a raw material, powder is periodically spread layer by layer along a certain direction, and blank ink, coloring ink with different solute concentrations and anti-reflection ink with different solute concentrations are selectively, respectively, simultaneously or alternately, subjected to ink-jet printing and superposed layer by layer to prepare the zirconia ceramic block for the all-ceramic denture, the color and/or the light transmittance of which are quasi-continuously changed from one side to the other side of the certain direction;
the zirconia ceramic block for the full-ceramic false tooth with quasi-continuous change of color and light transmittance is prepared by adopting an ink-jet additive manufacturing technology, and the preparation process comprises the following steps:
(1) one or more partially stabilized zirconia powders containing different mole percentages of yttria, ceria, magnesia, scandia, samaria, ytterbia and/or calcium oxide stabilizers are used as main preparation raw materials of the zirconia ceramic block for the full-ceramic denture; one or more CeO with different concentrations are adopted2、Fe2O3、Mn2O3、Pr2O3、Er2O3、TiO2、GeO2、ZrO2、Al2O3、CaO、CuO、Co3O4、NiO、V2O5、Cr2O3、In2O3、Dy2O3、Eu2O3、Ga2O3、Ho2O3、Tb2O3、RuO2、SnO2、Bi2O3And/or Tm2O3Aqueous, non-aqueous or photocurable suspensions of nano-metal oxide powders, or containing different concentrations of Ce4+、Fe3+、Mn3+、Pr3+、Er3+、Ti4+、Ge4+、Zr4+、Al3+、Ca2+、Cu2+、Co2+、Co3+、Ni2+、V5+、Cr3+、In3+、Dy3+、Eu3+、Ga3+、Ho3+、Tb3+、Ru4+、Sn4+、Bi3+And/or Tm3+Ionic aqueous, non-aqueous or photocurable solutions as coloring inks; one or more than one of Y with different concentrations2O3、La2O3、Sc2O3、Nd2O3、Yb2O3、Gd2O3、Sm2O3、Mn2O3、Er2O3、ThO2、TiO2、CeO2MgO, CaO and/or Al2O3Aqueous, non-aqueous metal oxide nanopowdersAqueous or photocurable suspensions, or different concentrations of Y3+、La3+、Sc3+、Nd3+、Yb3+、Gd3+、Sm3+、Mn3+、Er3+、Th4+、Ti4+、Ce4+、Mg2+、Ca2+And/or Al3+Ionic aqueous, non-aqueous or photocurable solutions as antireflective inks;
(2) filling blank ink which does not contain any nano oxide powder and/or any metal ions and contains aqueous, non-aqueous or photo-curing binder and humectant, quick drying agent, lubricant, coagulant, flow promoter, defoaming agent and pH regulator into 1 special ink box;
(3) one or more than one coloring ink is put into 1 ink box or a plurality of ink boxes respectively;
(4) one or more anti-reflection ink is put into 1 ink box or a plurality of ink boxes respectively;
(5) one or more than one partially stabilized zirconia powder is put into 1 powder box or a plurality of powder boxes respectively;
(6) according to the gradient requirement of quasi-continuous change of the color and the light transmittance of a product and the specification and the size of the product, determining the size of a two-dimensional printing section, the single descending stroke of a working platform or the thickness of an ink-jet printing layer, calculating the total number of the ink-jet printing layers, and driving at least 1 powder box to spread powder along the horizontal direction by a linear motor and leveling the powder by a scraper;
(7) determining the solute type and concentration of the permeation ink and/or the coloring ink and/or the blank ink, the number of ink boxes and ink-jet printing parameters according to the gradient requirement of quasi-continuous change of color and light transmittance;
(8) according to the gradient requirement of quasi-continuous change of color and light transmittance of the zirconia ceramic block for the full-ceramic false tooth, based on the adopted blank ink, anti-reflection ink and coloring ink with various solute types and concentrations, the number of ink boxes and set ink-jet printing parameters, according to the single-layer thickness and the two-dimensional printing section size of the printing layer of the zirconia ceramic block blank for the full-ceramic false tooth, the linear motor drives the ink-jet printing head to move forward and backward and spray the blank ink and the anti-reflection ink and the coloring ink with various solute types and concentrations, powder is selectively paved in the vertical direction of the two-dimensional printing section in sequence, and ink-jet printing is selectively performed layer by layer respectively or simultaneously or alternately according to the set two-dimensional printing section, after one-layer printing is completed, the working platform descends by a stroke of the thickness of the printing layer, and then powder spreading and ink jet printing are carried out in a circulating and alternating manner until all layers of the whole product are printed;
(9) after the ink-jet printing is finished, taking out the printed zirconium oxide ceramic block blank for the all-ceramic false tooth, cleaning floating powder on the surface of the blank, and then carrying out cold isostatic pressing and reshaping after carrying out vacuum plastic package on the blank;
(10) placing the blank after cold isostatic pressing and reshaping into a box-type electric furnace, slowly heating for degreasing and presintering;
(11) according to the product specification requirements, the zirconium oxide ceramic block for the complete ceramic false tooth with the color and/or the light transmittance which are quasi-continuously changed along a determined direction is obtained after machining.
8. The preparation process of the zirconia ceramic block for the all-ceramic denture according to claim 7, wherein before the ink-jet printing, the descending stroke of the working platform or the thickness of the ink-jet printing layer is 5-500 μm according to the gradient requirement of quasi-continuous change of color and light transmittance, namely the thickness of the powder laying monolayer is 5-500 μm; the linear motor drives the powder box to spread powder along the horizontal direction and simultaneously uses a scraper to level the powder; before ink-jet printing, determining that pixels of a two-dimensional section of anti-reflection ink and colored ink and/or blank ink-jet printing are 0 multiplied by 0 to 2880 multiplied by 2880DPI and print repetition times PASS are 1 to 15 times according to the gradient requirement of quasi-continuous change of color and light transmittance.
9. The process for preparing a zirconia ceramic block for an all-ceramic denture according to claim 7, wherein partially stabilized zirconia powders containing yttria, ceria, magnesia, scandia, samaria, ytterbia and/or calcia are loaded into one or more powder cartridges separately or in combination according to the gradient requirement of quasi-continuous change of color and/or transmittance, and the blank of the zirconia ceramic block for an all-ceramic denture with quasi-continuous change of color and transmittance is obtained by controlling and changing the powder laying sequence of each powder cartridge, the single descending stroke of the working platform, the powder laying thickness of each layer, and the ink-jet printing parameters of each layer of permeation ink and/or coloring ink and/or blank ink.
10. The process for preparing the zirconia ceramic block for the all-ceramic denture according to claim 7, wherein the zirconia ceramic block blank for the all-ceramic denture taken out after the ink-jet printing is finished is subjected to cold isostatic pressing at 50MPa to 350MPa for reshaping, and the zirconia ceramic block blank for the all-ceramic denture subjected to the cold isostatic pressing is subjected to degreasing at 200 to 650 ℃ and presintering at 850 to 1350 ℃.
11. The process for producing a zirconia ceramic block for an all-ceramic denture according to claim 7, wherein the relative density of the zirconia ceramic block blank for an all-ceramic denture taken out after the completion of the ink-jet printing after the cold isostatic pressing is more than 50%.
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