CN112062560A - Medical composite ceramic material and preparation method thereof - Google Patents
Medical composite ceramic material and preparation method thereof Download PDFInfo
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- CN112062560A CN112062560A CN202010941200.2A CN202010941200A CN112062560A CN 112062560 A CN112062560 A CN 112062560A CN 202010941200 A CN202010941200 A CN 202010941200A CN 112062560 A CN112062560 A CN 112062560A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 160
- 239000000919 ceramic Substances 0.000 claims abstract description 111
- 239000000843 powder Substances 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000003086 colorant Substances 0.000 claims abstract description 39
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 59
- 235000015895 biscuits Nutrition 0.000 claims description 50
- 238000000498 ball milling Methods 0.000 claims description 44
- 238000005245 sintering Methods 0.000 claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 239000002270 dispersing agent Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 27
- 239000002518 antifoaming agent Substances 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 238000000016 photochemical curing Methods 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- -1 acyl phosphine oxide Chemical compound 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000010146 3D printing Methods 0.000 claims description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 238000005452 bending Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 5
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
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- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007704 transition Effects 0.000 abstract description 6
- 238000004513 sizing Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 239000011351 dental ceramic Substances 0.000 description 3
- 208000008312 Tooth Loss Diseases 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 210000004513 dentition Anatomy 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 210000000936 intestine Anatomy 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- 230000036346 tooth eruption Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 206010008190 Cerebrovascular accident Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 208000006011 Stroke Diseases 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 208000010643 digestive system disease Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000021059 hard food Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention provides a medical composite ceramic material and a preparation method thereof, wherein the medical composite ceramic material comprises at least three ceramic layers with the color changing from deep to light in a gradient manner from the neck to the cut end, and the color gradient difference value of the two adjacent ceramic layers is less than or equal to 10 percent; the ceramic layer comprises zirconia ceramic powder, a coloring agent, light-cured resin, a photoinitiator and an auxiliary agent; the total mass of the zirconia ceramic powder and the coloring agent of each ceramic layer is 100 wt%, the zirconia ceramic powder in the neck ceramic layer accounts for 80-90 wt%, and the rest is the coloring agent; the zirconia ceramic powder contained in each ceramic layer from the neck to the cutting end gradually increases according to the gradient of 5-10 wt%. The ceramic material prepared by the invention has gradient color change, natural color transition, color distribution characteristics close to natural teeth, simple preparation process, stable effect and easy operation.
Description
Technical Field
The invention belongs to the technical field of medical ceramic materials, relates to a medical composite ceramic material and a preparation method thereof, and particularly relates to a medical composite ceramic material with gradient color change and a preparation method thereof.
Background
Teeth are an organ of a human body, and long-term defects cause great harm to the human body. After the loss of teeth, the alveolar bone is seriously absorbed for a long time due to the loss of normal occlusion. Simultaneously, the upper and lower jaws lose the support of teeth, which can cause the face to collapse and affect the face appearance, so that people can look old. Meanwhile, the loss of teeth causes the reduction of the chewing function, and the food is not easy to chew. The un-chewed food enters intestines and stomach, increases the burden of the intestines and stomach and causes digestive system diseases. If a plurality of teeth are lost, the speech function is affected, and the phenomena of speech leakage, unclear word biting and the like are caused. In addition, statistics of oral medical data show that the lack of teeth has great relationship with coronary heart disease, diabetes, senile dementia, apoplexy, respiratory diseases and the like.
In recent years, all-ceramic tooth repairing products are favored by people, but all-ceramic teeth have many defects which cannot be avoided. Firstly, the traditional full-porcelain tooth product has high hardness, and jaw teeth are easily damaged in daily life and use. Secondly, the whole porcelain tooth product has high brittleness, and the porcelain is easy to crack when the whole porcelain tooth product bites hard food. Thirdly, the traditional all-ceramic tooth needs to be colored in the later period, the color gradient of the natural tooth is difficult to achieve through multiple dyeing steps, and the problems of uneven dyeing, unobvious transition and the like can occur in the operation process. This makes it difficult to achieve a perfect aesthetic restoration of a conventional dental prosthesis.
The zirconia ceramics as the oral cavity all-ceramic repairing material has the characteristics similar to natural teeth in the aspects of biocompatibility, chemical stability, bending strength and the like, so that the zirconia ceramics is recommended to be used as the repairing material matched with the natural teeth. However, a perfect restoration has the advantages that the mechanical property, the shape and the size of the restoration need to meet the clinical requirements, and the color of the restoration can be close to that of a natural tooth. However, most of the currently prepared dental zirconia ceramic restoration materials have single color and cannot meet the color distribution characteristics of natural teeth.
CN111136915A discloses a mechanical and aesthetic gradient gradual change denture integrated design and 3D printing method, which comprises the following steps: designing a dentition part and a base part of the denture by using CAD software; dividing dentition into 3-5 layers along the direction from the occlusal surface to the gum, wherein cross transition layers are arranged among the layers, and the hardness, the wear resistance and the color are in gradient transition; dividing the base into an upper layer and a lower layer 2 along the direction from the occlusal surface to the gum, and performing gradient transition on hardness and color; according to the personalized clinical colorimetric result of the teeth of a patient, color layers distinguished by color models are set in the normal direction of a plane (occlusal) and each layer represents a color, and the starting and stopping surface of each color layer (occlusal) in the normal direction of the plane is marked to be used as an interface for replacing different materials; and (4) applying numerical control processing equipment and matched software thereof to implement false tooth printing and forming so as to finish the manufacture of the false tooth.
CN103058655B discloses a gradient transparent zirconia dental ceramic and a preparation method thereof, wherein the raw material is formed by mixing 2-5 zirconia ceramic powders with different sintering transparencies. The transparency of the sintered zirconia ceramic is gradually increased from the bottom end to the top end, and the sintered zirconia ceramic comprises 5-11 ceramic layers with different transparencies. The preparation method comprises five steps of preparing mixed powder, dry pressing and forming, cold isostatic pressing and forming, pre-sintering and blank body repairing.
CN108992355A discloses a method for manufacturing a dental restoration zirconia block with color gradient of each layer, comprising: a main raw material separation step (S10) for pulverizing zirconia into different particle sizes, and preparing the zirconia by classifying the particle sizes; an auxiliary material mixing step (S20) of charging and mixing auxiliary materials capable of adjusting water absorption into main materials having respective different particle sizes; a raw material pressurizing step (S30) in which a main raw material mixed with an auxiliary raw material is fed into a compression molding die in the order of a larger particle size or in the order of a smaller particle size, and then compression-molded into a block shape; a raw material coloring step (S40) of putting the molded zirconia block into a water tank saturated with a color solution and then inducing the color solution to permeate into the zirconia block by heating; and a heat treatment ending step (S50) of drying the zirconia block infiltrated with the color solution and then calcining the same with heat at normal temperature.
Therefore, the dental zirconia ceramic repair material which has an obvious color gradient effect and meets the color distribution characteristics of natural teeth needs to be prepared so as to simulate the color of the natural teeth and greatly increase the aesthetic effect of the dental zirconia ceramic.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a medical composite ceramic material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a medical composite ceramic material, which comprises at least three ceramic layers with the color changing from deep to light in a gradient manner from the neck to the cut end, and the color gradient difference value of the two adjacent ceramic layers is less than or equal to 10%.
The ceramic layer comprises zirconia ceramic powder, a coloring agent, light-cured resin, a photoinitiator and an auxiliary agent.
The zirconia ceramic powder in the neck portion ceramic layer accounts for 80-90 wt%, for example, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt% or 90 wt%, based on 100 wt% of the total mass of the zirconia ceramic powder and the coloring agent in each ceramic layer, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable, and the remainder is the coloring agent. The zirconia ceramic powder contained in each ceramic layer from the neck portion to the cut end is gradually increased by 5 to 10 wt%, and may be, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The ceramic material prepared by the invention has gradient color change, natural color transition, color distribution characteristics close to natural teeth, simple preparation process, stable effect and easy operation.
In a preferred embodiment of the present invention, the photocurable resin is 25 to 50 wt% of the zirconia ceramic powder, for example, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the photoinitiator is 5 to 10 wt% of the mass of the photocurable resin, such as 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme, the auxiliary agent comprises a dispersing agent, a leveling agent and a defoaming agent.
Preferably, the dispersant is 1 to 5 wt% of the zirconia ceramic powder, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the leveling agent is 1 to 5 wt% of the mass of the photo-curable resin, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the defoaming agent is 1 to 5 wt% of the mass of the photocurable resin, such as 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the coloring agent comprises Fe2O3、Pr2O3Or Er2O3Or a combination of at least two thereof.
The coloring agent adopted by the invention is rare earth oxide or transition metal oxide, the zirconium oxide ceramic is mixed and colored by the coloring agent, and the transition metal oxide can form a color structure when entering ZrO2 crystal lattice, so that the zirconium oxide ceramic with natural tooth color is obtained.
Preferably, the light-cured resin comprises one or a combination of at least two of epoxy acrylate, polyurethane acrylate, polyester acrylate and polyether acrylate.
Preferably, the photoinitiator comprises one or a combination of at least two of 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, benzophenone, methyl benzoylformate and acyl phosphine oxide.
Preferably, the dispersant is a polymeric dispersant, and further preferably, the dispersant comprises one or a combination of at least two of polyacrylic acid derivatives, polycarboxylate, polyvinylpyrrolidone, polyether derivatives or polyethylene glycol.
Compared with the traditional small molecular dispersing agent, the solid group and the solvent chain contained in the macromolecular dispersing agent respectively replace the hydrophilic group and the lipophilic group in the small molecular dispersing agent. The lipophilic group of the common micromolecule dispersant is a short-chain alkane structure, so that a sufficient space position resistance layer is difficult to form, the macromolecular dispersant makes up for the defects of the micromolecule dispersant, the anchoring group of the molecular chain can be adsorbed on the surface of the ceramic particle in a single-point adsorption or multi-point anchoring mode through the mutual interaction of ionic bonds, covalent bonds, hydrogen bonds, Van der Waals force and the like, and the longer solvation chain at the other end of the molecular chain is stretched and dissociated in the photosensitive resin.
Preferably, the leveling agent is polyacrylate.
Preferably, the defoaming agent is polyether modified polydimethylsiloxane.
In a preferred embodiment of the present invention, the zirconia ceramic powder has a particle size of 500nm to 50000nm, for example, 500nm, 1000nm, 5000nm, 10000nm, 15000nm, 20000nm, 25000nm, 30000nm, 35000nm, 40000nm, 45000nm or 50000nm, but the particle size is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the zirconia ceramic powder has a porosity of 25 to 35%, for example 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
In a preferred embodiment of the present invention, the medical composite ceramic material has a flexural strength of 200MPa or more, and may be, for example, 200MPa, 210MPa, 220MPa, 230MPa, 240MPa, 250MPa, 260MPa, 270MPa, 280MPa, 290MPa or 300MPa, but the present invention is not limited to the above numerical values, and other numerical values not listed in the numerical values range are also applicable.
Preferably, the medical composite ceramic material has a hardness of 0.5 to 3.5GPa, for example, 0.5GPa, 1GPa, 1.5GPa, 2GPa, 2.5GPa, 3GPa or 3.5GPa, but the hardness is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the density of the medical composite ceramic material is 1.5-2.5 g/cm3For example, it may be 1.5g/cm3、1.6g/cm3、1.7g/cm3、1.8g/cm3、1.9g/cm3、2.0g/cm3、2.1g/cm3、2.2g/cm3、2.3g/cm3、2.4g/cm3Or 2.5g/cm3However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
In a second aspect, the invention provides a preparation method of a medical composite ceramic material, which comprises the following steps:
mixing zirconia ceramic powder, a coloring agent, a light-cured resin, a photoinitiator and an auxiliary agent in proportion to prepare at least three parts of slurry with equal mass, wherein the total mass of the zirconia ceramic powder and the coloring agent in each part of slurry is 100 wt%, the mass fraction of the zirconia ceramic powder in the slurry with the deepest color is 80-90 wt%, and the balance is the coloring agent; according to the sequence of the color from deep to light, the quality of the zirconia ceramic powder in each slurry is gradually increased by 5-10 wt% in an isocratic way;
and (II) sequentially injecting the slurry into a light curing forming device according to the sequence of the color from deep to light, preparing a biscuit through light curing 3D printing, and sequentially degreasing and sintering the biscuit to obtain the composite ceramic material.
The invention prepares a biscuit by 3D printing technology according to the depth of slurry containing zirconia ceramic powder with different percentages, and then carries out degreasing sintering on the biscuit to obtain the zirconia dental ceramic restoration with the color gradient change and the color distribution characteristic close to that of natural teeth. The color of the prosthesis prepared by the invention is changed in a gradient way, the color is transited naturally and is close to the color distribution characteristic of natural teeth, the preparation process is simple, the effect is stable, and the operation is easy.
In a preferred embodiment of the present invention, in step (i), the photocurable resin is 25 to 50 wt%, for example, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt% of the zirconia ceramic powder, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the photoinitiator is 5 to 10 wt% of the mass of the photocurable resin, such as 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the auxiliary agent comprises a dispersing agent, a leveling agent and an antifoaming agent;
preferably, the dispersant is 1 to 5 wt% of the zirconia ceramic powder, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the leveling agent is 1 to 5 wt% of the mass of the photo-curable resin, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the defoaming agent is 1 to 5 wt% of the mass of the photocurable resin, such as 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the coloring agent comprises Fe2O3、Pr2O3Or Er2O3Or a combination of at least two thereof.
Preferably, the light-cured resin comprises one or a combination of at least two of epoxy acrylate, polyurethane acrylate, polyester acrylate and polyether acrylate.
Preferably, the photoinitiator comprises one or a combination of at least two of 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, benzophenone, methyl benzoylformate and acyl phosphine oxide.
Preferably, the dispersant is a polymeric dispersant, and further preferably, the dispersant comprises one or a combination of at least two of polyacrylic acid derivatives, polycarboxylate, polyvinylpyrrolidone, polyether derivatives or polyethylene glycol.
Preferably, the leveling agent is polyacrylate.
Preferably, the defoaming agent is polyether modified polydimethylsiloxane.
Preferably, the zirconia ceramic powder has a particle size of 500nm to 50000nm, for example, 500nm, 1000nm, 5000nm, 10000nm, 15000nm, 20000nm, 25000nm, 30000nm, 35000nm, 40000nm, 45000nm or 50000nm, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the zirconia ceramic powder has a porosity of 25 to 35%, for example 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
In a preferred technical scheme of the invention, in step (i), the zirconia ceramic powder, the coloring agent, the light-cured resin, the photoinitiator and the auxiliary agent are mixed and ball-milled in proportion to obtain the slurry.
Preferably, the ball milling time is 4 to 8 hours, for example, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the order of addition of the raw materials is: firstly, mixing a coloring agent, light-cured resin and an auxiliary agent, carrying out primary ball milling to obtain a mixed solution, and then adding a photoinitiator and zirconia ceramic powder into the mixed solution, and carrying out secondary ball milling to obtain the slurry.
Preferably, the rotation speed of the primary ball milling is 800-1000 rpm/min, such as 800rpm/min, 810rpm/min, 820rpm/min, 830rpm/min, 840rpm/min, 850rpm/min, 860rpm/min, 870rpm/min, 880rpm/min, 890rpm/min, 900rpm/min or 1000rpm/min, but not limited to the enumerated values, and other non-enumerated values within the range of the enumerated values are also applicable.
Preferably, the time of the primary ball milling is 4 to 6 hours, for example, 4.0 hours, 4.5 hours, 5.0 hours, 5.5 hours or 6.0 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the rotation speed of the secondary ball milling is 800 to 1000rpm/min, such as 800rpm/min, 810rpm/min, 820rpm/min, 830rpm/min, 840rpm/min, 850rpm/min, 860rpm/min, 870rpm/min, 880rpm/min, 890rpm/min, 900rpm/min or 1000rpm/min, but not limited to the enumerated values, and other non-enumerated values within the range of the enumerated values are also applicable.
Preferably, the time of the secondary ball milling is 1 to 2 hours, for example, 1.0 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2.0 hours, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferred technical solution of the present invention, in the step (ii), the degreasing process includes: the temperature of the green body is raised to 500 to 700 ℃ and the green body is then kept warm, and the photo-curable resin is removed therefrom, for example, by raising the temperature to 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃ or 700 ℃, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the temperature increase rate of the degreasing process is 2.5-3 ℃/min, such as 2.5 ℃/min, 2.6 ℃/min, 2.7 ℃/min, 2.8 ℃/min, 2.9 ℃/min or 3.0 ℃/min, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the incubation time of the degreasing process is 2-3 h, for example, 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical solution of the present invention, in step (ii), the sintering process includes: and sequentially pre-sintering and secondary sintering the degreased biscuit to obtain a ceramic biscuit.
Preferably, the pre-sintering process comprises: the green body is heated from 500 to 700 ℃ to 1000 to 1200 ℃ and then heat-preserved, for example, to 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃, 1090 ℃, 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃, 1190 ℃ or 1200 ℃, but the temperature is not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the temperature increase rate of the pre-sintering process is 5-10 ℃/min, such as 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the holding time of the pre-sintering process is 1 to 4 hours, for example, 1 hour, 2 hours, 3 hours or 4 hours, but not limited to the recited values, and other values in the range are also applicable.
Preferably, the secondary sintering process comprises: the pre-sintered green body is heated from 1000 to 1200 ℃ to 1400 to 1600 ℃ and then heat-preserved, for example, to 1400 ℃, 1410 ℃, 1420 ℃, 1430 ℃, 1440 ℃, 1450 ℃, 1460 ℃, 1470 ℃, 1480 ℃, 1490 ℃, 1500 ℃, 1510 ℃, 1520 ℃, 1530 ℃, 1540 ℃, 1550 ℃, 1560 ℃, 1570 ℃, 1580 ℃, 1590 ℃ or 1600 ℃, but not limited to the values listed, and other values not listed within this range are also applicable.
Preferably, the temperature increase rate of the secondary sintering is 5 to 10 ℃/min, for example, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the holding time of the secondary sintering is 1 to 3 hours, for example, 1.0 hour, 1.5 hours, 2.0 hours, 2.5 hours or 3.0 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares a biscuit by 3D printing technology according to the depth of slurry containing zirconia ceramic powder with different percentages, and then carries out degreasing sintering on the biscuit to obtain the zirconia dental ceramic restoration with the color gradient change and the color distribution characteristic close to that of natural teeth. The color of the prosthesis prepared by the invention is changed in a gradient way, the color is transited naturally and is close to the color distribution characteristic of natural teeth, the preparation process is simple, the effect is stable, and the operation is easy.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of a medical composite ceramic material, which comprises the following steps:
(1) 6 parts of equal mass of slurry are prepared and respectively marked as slurry a, slurry b, slurry c, slurry d, slurry e and slurry f, and the color of the slurry a-f is from dark to light. Each part of slurry comprises zirconia ceramic powder, a coloring agent, a light-cured resin, a photoinitiator, a dispersing agent, a flatting agent and a defoaming agent, and the mass of each component in each part of slurry is as follows:
wherein the particle diameter of the zirconia ceramic powder is 500nm, the porosity of the zirconia ceramic powder is 25 percent, and the staining agent is Fe2O3The photo-curing resin is epoxy acrylate, the photoinitiator is 1-hydroxy cyclohexyl phenyl ketone, the dispersing agent is polyacrylic acid derivative, the leveling agent is polyacrylate, and the defoaming agent is polyether modified polydimethylsiloxane;
(2) the raw materials weighed according to the proportion are used for standby, firstly, the coloring agent, the light-cured resin and the auxiliary agent are mixed, mixed liquor is obtained after primary ball milling, and then the photoinitiator and the zirconia ceramic powder are added into the mixed liquor, and the slurry is obtained after secondary ball milling; the rotating speed of the primary ball milling is 800rpm/min, the time of the primary ball milling is 4 hours, the rotating speed of the secondary ball milling is 800rpm/min, and the time of the secondary ball milling is 1 hour;
(3) sequentially injecting the slurry into a photocuring forming device according to the sequence of the slurries a-f, and carrying out photocuring 3D printing to obtain a biscuit;
(4) heating the biscuit to 500 ℃ at the heating rate of 2.5 ℃/min, then preserving the heat for 2h, and removing the light-cured resin in the biscuit;
(5) sequentially pre-sintering and secondary sintering the degreased biscuit to obtain a ceramic biscuit; the pre-sintering process comprises the following steps: heating the biscuit from 500 ℃ to 1000 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 1 h; the secondary sintering process comprises the following steps: and heating the pre-sintered biscuit from 1000 ℃ to 1400 ℃ at the heating rate of 5 ℃/min, and then preserving heat for 1h to prepare the ceramic material restoration.
The ceramic material prosthesis finally prepared comprises 6 ceramic layers with the color changing from deep to light in a gradient way from the neck to the cutting end, the color gradient difference value of the two adjacent ceramic layers is 6 percent, the bending strength of the ceramic material prosthesis is 220MPa, the hardness is 1.8GPa, and the density is 1.5g/cm3。
Example 2
The embodiment provides a preparation method of a medical composite ceramic material, which comprises the following steps:
(1) four parts of sizing agents with equal mass are prepared and respectively marked as sizing agent a, sizing agent b, sizing agent c and sizing agent d, and the colors of the sizing agents a-d are from dark to light. Each part of slurry comprises zirconia ceramic powder, a coloring agent, a light-cured resin, a photoinitiator, a dispersing agent, a flatting agent and a defoaming agent, and the mass of each component in each part of slurry is as follows:
the grain diameter of the zirconia ceramic powder is 20000nm, the porosity of the zirconia ceramic powder is 27 percent, and the staining agent is Pr2O3The photo-curing resin is polyurethane acrylate, the photoinitiator is benzoin dimethyl ether, the dispersing agent comprises polycarboxylate, the flatting agent is polyacrylate, and the defoaming agent is polyether modified polydimethylsiloxane;
(2) the raw materials weighed according to the proportion are used for standby, firstly, the coloring agent, the light-cured resin and the auxiliary agent are mixed, mixed liquor is obtained after primary ball milling, and then the photoinitiator and the zirconia ceramic powder are added into the mixed liquor, and the slurry is obtained after secondary ball milling; the rotating speed of the primary ball milling is 850rpm/min, and the time of the primary ball milling is 4.5 h; the rotation speed of the secondary ball milling is 850rpm/min, and the time of the secondary ball milling is 1.2 h;
(3) sequentially injecting the slurry into a photocuring forming device according to the sequence of the slurries a-D, and carrying out photocuring 3D printing to obtain a biscuit;
(4) heating the biscuit to 550 ℃ at the heating rate of 2.7 ℃/min for 2.3h, and removing the photocuring resin in the biscuit;
(5) sequentially pre-sintering and secondary sintering the degreased biscuit to obtain a ceramic biscuit; the pre-sintering process comprises the following steps: heating the biscuit from 550 ℃ to 1050 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 2 h; the secondary sintering process comprises the following steps: and heating the pre-sintered biscuit from 1050 ℃ to 1450 ℃ at a heating rate of 7 ℃/min, and then preserving the heat for 1.5h to prepare the ceramic material prosthesis.
The ceramic material prosthesis finally prepared comprises 4 ceramic layers with the color changing from deep to light in a gradient way from the neck to the cutting end, the color gradient difference value of the two adjacent ceramic layers is 7 percent, and the ceramic material prosthesis has strong bending resistanceThe hardness is 250MPa, the hardness is 2.2GPa, and the density is 2g/cm3And preparing the ceramic material prosthesis.
Example 3
The embodiment provides a preparation method of a medical composite ceramic material, which comprises the following steps:
(1) preparing 4 parts of sizing agents with equal mass, and respectively marking the sizing agents as sizing agent a, sizing agent b, sizing agent c and sizing agent d, wherein the colors of the sizing agents a-d are from dark to light. Each part of slurry comprises zirconia ceramic powder, a coloring agent, a light-cured resin, a photoinitiator, a dispersing agent, a flatting agent and a defoaming agent, and the mass of each component in each part of slurry is as follows:
the grain diameter of the zirconia ceramic powder is 30000nm, the porosity of the zirconia ceramic powder is 30 percent, and the coloring agent is Er2O3(ii) a The photocuring resin is polyester acrylate, the photoinitiator is benzophenone, the dispersant is polyvinylpyrrolidone, the leveling agent is polyacrylate, and the defoaming agent is polyether modified polydimethylsiloxane;
(2) the raw materials weighed according to the proportion are used for standby, firstly, the coloring agent, the light-cured resin and the auxiliary agent are mixed, mixed liquor is obtained after primary ball milling, and then the photoinitiator and the zirconia ceramic powder are added into the mixed liquor, and the slurry is obtained after secondary ball milling; the rotating speed of the primary ball milling is 900rpm/min, and the time of the primary ball milling is 5 hours; the rotation speed of the secondary ball milling is 900rpm/min, and the time of the secondary ball milling is 1.5 h;
(3) sequentially injecting the slurry into a photocuring forming device according to the sequence of the slurries a-D, and carrying out photocuring 3D printing to obtain a biscuit;
(4) heating the biscuit to 600 ℃ at the heating rate of 2.8 ℃/min, then preserving the heat for 2.5h, and removing the light-cured resin in the biscuit;
(5) sequentially pre-sintering and secondary sintering the degreased biscuit to obtain a ceramic biscuit; the pre-sintering process comprises the following steps: the biscuit is heated from 600 ℃ to 1100 ℃ at the heating rate of 8 ℃/min and then is kept for 2.5 h; the secondary sintering process comprises the following steps: and heating the pre-sintered biscuit from 1100 ℃ to 1500 ℃ at the heating rate of 2.5 ℃/min, and then preserving heat for 2h to prepare the ceramic material prosthesis.
The ceramic material prosthesis finally prepared comprises 4 ceramic layers with the color changing from deep to light in a gradient way from the neck to the cutting end, the color gradient difference value of the two adjacent ceramic layers is 8 percent, the bending strength of the ceramic material prosthesis is 310MPa, the hardness is 3.5GPa, and the density is 2.5g/cm3。
Example 4
The embodiment provides a preparation method of a medical composite ceramic material, which comprises the following steps:
(1) 3 parts of equal mass of slurry are prepared and respectively marked as slurry a, slurry b and slurry c, and the color of the slurry a-c is from dark to light. Each part of slurry comprises zirconia ceramic powder, a coloring agent, a light-cured resin, a photoinitiator, a dispersing agent, a flatting agent and a defoaming agent, and the mass of each component in each part of slurry is as follows:
the grain diameter of the zirconia ceramic powder is 40000nm, the porosity of the zirconia ceramic powder is 32 percent, and the staining agent is Fe2O3(ii) a The photocuring resin is polyether acrylate, the photoinitiator is methyl benzoylformate, the dispersant is a polyether derivative, the leveling agent is polyacrylate, and the defoaming agent is polyether modified polydimethylsiloxane;
(2) the raw materials weighed according to the proportion are used for standby, firstly, the coloring agent, the light-cured resin and the auxiliary agent are mixed, mixed liquor is obtained after primary ball milling, and then the photoinitiator and the zirconia ceramic powder are added into the mixed liquor, and the slurry is obtained after secondary ball milling; the rotating speed of the primary ball milling is 950rpm/min, and the time of the primary ball milling is 5.5 h; the rotation speed of the secondary ball milling is 950rpm/min, and the time of the secondary ball milling is 1.7 h;
(3) sequentially injecting the slurry into a photocuring forming device according to the sequence of the slurries a to c, and carrying out photocuring 3D printing to obtain a biscuit;
(4) heating the biscuit to 650 ℃ at the heating rate of 2.9 ℃/min, then preserving the heat for 2.7h, and removing the light-cured resin in the biscuit;
(5) sequentially pre-sintering and secondary sintering the degreased biscuit to obtain a ceramic biscuit; the pre-sintering process comprises the following steps: heating the biscuit from 650 ℃ to 1150 ℃ at a heating rate of 9 ℃/min, and then preserving heat for 3 h; the secondary sintering process comprises the following steps: and heating the pre-sintered biscuit from 1150 ℃ to 1550 ℃ at the heating rate of 9 ℃/min, and then preserving heat for 2.5h to prepare the ceramic material prosthesis.
The ceramic material prosthesis finally prepared comprises 3 ceramic layers with the color changing from deep to light in a gradient way from the neck to the cutting end, the color gradient difference value of the two adjacent ceramic layers is 9 percent, the bending strength of the ceramic material prosthesis is 330MPa, the hardness is 3.2GPa, and the density is 2g/cm3And preparing the ceramic material prosthesis.
Example 5
The embodiment provides a preparation method of a medical composite ceramic material, which comprises the following steps:
(1) preparing 3 parts of slurry with equal mass, which is respectively marked as slurry a, slurry b and slurry c, wherein the colors of the slurry a to c are from dark to light, each part of slurry comprises zirconia ceramic powder, a coloring agent, a light-cured resin, a photoinitiator, a dispersing agent, a leveling agent and a defoaming agent, and the mass of each component in each part of slurry is as follows:
the grain diameter of the zirconia ceramic powder is 50000nm, the porosity of the zirconia ceramic powder is 35 percent, and the staining agent is Pr2O3The light-cured resin is epoxy acrylateThe photoinitiator is acyl phosphine oxide, the dispersant is polyethylene glycol, the flatting agent is polyacrylate, and the defoaming agent is polyether modified polydimethylsiloxane;
(2) the raw materials weighed according to the proportion are used for standby, firstly, the coloring agent, the light-cured resin and the auxiliary agent are mixed, mixed liquor is obtained after primary ball milling, and then the photoinitiator and the zirconia ceramic powder are added into the mixed liquor, and the slurry is obtained after secondary ball milling; the rotating speed of the primary ball milling is 1000rpm/min, and the time of the primary ball milling is 6 hours; the rotation speed of the secondary ball milling is 1000rpm/min, and the time of the secondary ball milling is 2 hours;
(3) sequentially injecting the slurry into a photocuring forming device according to the sequence of the slurries a to c, and carrying out photocuring 3D printing to obtain a biscuit;
(4) heating the biscuit to 700 ℃ at a heating rate of 3 ℃/min, then preserving heat for 3h, and removing the photocuring resin in the biscuit;
(5) sequentially pre-sintering and secondary sintering the degreased biscuit to obtain a ceramic biscuit; the pre-sintering process comprises the following steps: heating the biscuit from 700 ℃ to 1200 ℃ at a heating rate of 10 ℃/min, and then preserving heat for 4 h; the secondary sintering process comprises the following steps: and heating the pre-sintered biscuit from 1200 ℃ to 1600 ℃ at a heating rate of 10 ℃/min, and then preserving heat for 3h to prepare the ceramic material restoration.
The ceramic material prosthesis finally prepared comprises 3 ceramic layers with the color changing from deep to light in a gradient manner from the neck to the cutting end, the color gradient difference value of the two adjacent ceramic layers is 10 percent, the bending strength of the ceramic material prosthesis is 300MPa, the hardness is 1.9GPa, and the density is 1.8g/cm3And preparing the ceramic material prosthesis.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The medical composite ceramic material is characterized by comprising at least three ceramic layers with the color changing from deep to light in a gradient manner from the neck to the cut end, wherein the color gradient difference value of the two adjacent ceramic layers is less than or equal to 10 percent;
the ceramic layer comprises zirconia ceramic powder, a coloring agent, light-cured resin, a photoinitiator and an auxiliary agent;
the total mass of the zirconia ceramic powder and the coloring agent of each ceramic layer is 100 wt%, the zirconia ceramic powder in the neck ceramic layer accounts for 80-90 wt%, and the rest is the coloring agent; the zirconia ceramic powder contained in each ceramic layer from the neck to the cutting end gradually increases according to the gradient of 5-10 wt%.
2. The medical composite ceramic material according to claim 1, wherein the light-cured resin accounts for 25-50 wt% of the zirconia ceramic powder;
preferably, the photoinitiator is 5-10 wt% of the mass of the light-cured resin;
preferably, the auxiliary agent comprises a dispersing agent, a leveling agent and an antifoaming agent;
preferably, the dispersant accounts for 1-5 wt% of the mass of the zirconia ceramic powder;
preferably, the leveling agent is 1-5 wt% of the mass of the light-cured resin;
preferably, the defoaming agent accounts for 1-5 wt% of the mass of the light-cured resin.
3. The medical composite ceramic material as claimed in claim 1 or 2, wherein the coloring agent comprises Fe2O3、Pr2O3Or Er2O3One or a combination of at least two of;
preferably, the light-cured resin comprises one or a combination of at least two of epoxy acrylate, polyurethane acrylate, polyester acrylate and polyether acrylate;
preferably, the photoinitiator comprises one or the combination of at least two of 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, benzophenone, methyl benzoylformate and acyl phosphine oxide;
preferably, the dispersant is a polymeric dispersant, and further preferably, the dispersant comprises one or a combination of at least two of polyacrylic acid derivatives, polycarboxylate, polyvinylpyrrolidone, polyether derivatives or polyethylene glycol;
preferably, the leveling agent is polyacrylate;
preferably, the defoaming agent is polyether modified polydimethylsiloxane.
4. The medical composite ceramic material according to any one of claims 1 to 3, wherein the zirconia ceramic powder has a particle size of 500nm to 50000 nm;
preferably, the porosity of the zirconia ceramic powder is 25-35%.
5. The medical composite ceramic material according to any one of claims 1 to 4, wherein the bending strength of the medical composite ceramic material is not less than 200 MPa;
preferably, the hardness of the medical composite ceramic material is 0.5-3.5 GPa;
preferably, the density of the medical composite ceramic material is 1.5-2.5 g/cm3。
6. A method for preparing the medical composite ceramic material according to any one of claims 1 to 5, wherein the method comprises the following steps:
mixing zirconia ceramic powder, a coloring agent, a light-cured resin, a photoinitiator and an auxiliary agent in proportion to prepare at least three parts of slurry with equal mass, wherein the total mass of the zirconia ceramic powder and the coloring agent in each part of slurry is 100 wt%, the mass fraction of the zirconia ceramic powder in the slurry with the deepest color is 80-90 wt%, and the balance is the coloring agent; according to the sequence of the color from deep to light, the quality of the zirconia ceramic powder in each slurry is gradually increased by 5-10 wt% in an isocratic way;
and (II) sequentially injecting the slurry into a photocuring forming device according to the sequence of the color from deep to light, preparing a biscuit through photocuring 3D printing, and sequentially degreasing and sintering the biscuit to obtain the medical composite ceramic material.
7. The preparation method according to claim 6, wherein in the step (I), the light-cured resin accounts for 25-50 wt% of the mass of the zirconia ceramic powder;
preferably, the photoinitiator is 5-10 wt% of the mass of the light-cured resin;
preferably, the auxiliary agent comprises a dispersing agent, a leveling agent and an antifoaming agent;
preferably, the dispersant accounts for 1-5 wt% of the mass of the zirconia ceramic powder;
preferably, the leveling agent is 1-5 wt% of the mass of the light-cured resin;
preferably, the defoaming agent accounts for 1-5 wt% of the mass of the light-cured resin;
preferably, the coloring agent comprises Fe2O3、Pr2O3Or Er2O3One or a combination of at least two of;
preferably, the light-cured resin comprises one or a combination of at least two of epoxy acrylate, polyurethane acrylate, polyester acrylate and polyether acrylate;
preferably, the photoinitiator comprises one or the combination of at least two of-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, benzophenone, methyl benzoylformate and acylphosphine oxide;
preferably, the dispersant is a polymeric dispersant, and further preferably, the dispersant comprises one or a combination of at least two of polyacrylic acid derivatives, polycarboxylate, polyvinylpyrrolidone, polyether derivatives or polyethylene glycol;
preferably, the leveling agent is polyacrylate;
preferably, the defoaming agent is polyether modified polydimethylsiloxane;
preferably, the particle size of the zirconia ceramic powder is 500 nm-50000 nm;
preferably, the porosity of the zirconia ceramic powder is 25-35%.
8. The preparation method according to claim 6 or 7, wherein in the step (I), the zirconia ceramic powder, the coloring agent, the light-curing resin, the photoinitiator and the auxiliary agent are mixed and ball-milled according to a proportion to obtain the slurry;
preferably, the ball milling time is 4-8 h;
preferably, the order of addition of the raw materials is: firstly, mixing a coloring agent, a light-cured resin and an auxiliary agent, carrying out primary ball milling to obtain a mixed solution, and then adding a photoinitiator and zirconia ceramic powder into the mixed solution, carrying out secondary ball milling to obtain the slurry;
preferably, the rotation speed of the primary ball milling is 800-1000 rpm/min;
preferably, the time of the primary ball milling is 4-6 h;
preferably, the rotation speed of the secondary ball milling is 800-1000 rpm/min;
preferably, the time of the secondary ball milling is 1-2 h.
9. The method according to any one of claims 6 to 8, wherein in the step (II), the degreasing process comprises: heating the biscuit to 500-700 ℃, preserving heat, and removing the photocuring resin;
preferably, the temperature rise rate of the degreasing process is 2.5-3 ℃/min;
preferably, the heat preservation time of the degreasing process is 2-3 h.
10. The method according to any one of claims 6 to 9, wherein in the step (ii), the sintering process comprises: sequentially pre-sintering and secondary sintering the degreased biscuit to obtain a ceramic biscuit;
preferably, the pre-sintering process comprises: heating the biscuit from 500-700 ℃ to 1000-1200 ℃, and then preserving heat;
preferably, the temperature rise rate in the pre-sintering process is 5-10 ℃/min;
preferably, the heat preservation time of the pre-sintering process is 1-4 h;
preferably, the secondary sintering process comprises: raising the temperature of the pre-sintered biscuit from 1000-1200 ℃ to 1400-1600 ℃, and then preserving the heat;
preferably, the temperature rise rate of the secondary sintering is 5-10 ℃/min;
preferably, the heat preservation time of the secondary sintering is 1-3 h.
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