CN114213021B - Gradient bionic dental ceramic - Google Patents
Gradient bionic dental ceramic Download PDFInfo
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- CN114213021B CN114213021B CN202111608828.1A CN202111608828A CN114213021B CN 114213021 B CN114213021 B CN 114213021B CN 202111608828 A CN202111608828 A CN 202111608828A CN 114213021 B CN114213021 B CN 114213021B
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- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 19
- 239000011351 dental ceramic Substances 0.000 title claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 90
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- 229920003002 synthetic resin Polymers 0.000 claims description 7
- 239000000057 synthetic resin Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003592 biomimetic effect Effects 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 3
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 238000010146 3D printing Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 22
- 239000003921 oil Substances 0.000 description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 239000010687 lubricating oil Substances 0.000 description 15
- 239000002241 glass-ceramic Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000003103 lithium disilicate glass Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 230000008093 supporting effect Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 229910010293 ceramic material Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 244000241796 Christia obcordata Species 0.000 description 1
- 241000258955 Echinodermata Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 210000004268 dentin Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052907 leucite Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/833—Glass-ceramic composites
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/01—Other methods of shaping glass by progressive fusion or sintering of powdered glass onto a shaping substrate, i.e. accretion, e.g. plasma oxidation deposition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Materials Engineering (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Dental Prosthetics (AREA)
- Dental Preparations (AREA)
Abstract
The invention relates to a gradient bionic dental ceramic, comprising: the porous ceramic frame is of a TPMS structure, and a fully-communicated netlike through hole is formed in the porous ceramic frame; a polymer; wherein the polymer is filled in the netlike through holes. The beneficial effects of the invention are as follows: the porous ceramic frame with the TPMS structure is printed by adopting a 3D printing technology, the TPMS smooth full-communication porous structure has more excellent mechanical property and permeability, a perfect combination interface can be formed between the polymer and the porous ceramic frame, when the ceramic is stressed to generate cracks, the polymer filled by the porous structure can prevent the crack from expanding, the fracture toughness of the material is greatly improved, and meanwhile, the material is prevented from being invalid due to fatigue.
Description
Technical Field
The invention relates to the technical field of bionic teeth, in particular to gradient bionic dental ceramics.
Background
With the continuous improvement of aesthetic level of people, the demand for the aesthetic restoration of dentistry is increasing, but the commercial all-ceramic restoration material cannot meet the uniform balance of mechanical property and optical property required by the principle of aesthetic restoration, and becomes the bottleneck for restricting the development of the aesthetic restoration of dentistry. Currently, dental ceramic materials used clinically mainly include zirconia, alumina, glass ceramics, and the like.
Wherein the bending strength of the zirconia ceramic can reach 600-1200 MPa, and the fracture toughness can reach 6-15 MPa.m 1/2 As a nuclear ceramic material, the excellent mechanical property of the material is almost indiscriminate. However, zirconia has a poor light transmission performance compared with glass ceramics, and the Tp value of zirconia ceramics of different types is only between 5.5 and 15.1 (thickness of 1 mm), even lower than the light transmission performance of dentin (Tp value of 16). Second, zirconia hardness is much higher than natural teeth, and if in direct contact with natural teeth, excessive wear of the natural teeth can result. Zirconium oxide is currently the least aesthetically effective, limited by its lower light transmission properties and inherent high hardness, and is also limited to use as a nuclear ceramic material in the field of dental restorations.
The crystallization degree of the glass ceramic is controlled, so that polycrystalline solid with evenly distributed crystalline phase and glass phase can be prepared; after a certain heat treatment procedure, a part of glass phase in the matrix glass is converted into crystal phase, so that the strength of the material is improved; in addition, due to the existence of the glass phase, the glass ceramic shows good semi-light transmittance, and the gloss and light transmittance of natural teeth can be well simulated. Glass ceramics are mainly mica-based, leucite-based, lithium silicate-based, etc., depending on the substrate. Compared with zirconia and alumina ceramics, glass ceramics have very excellent aesthetic properties, and the refractive index of the crystal is very close to that of glass, so that the glass ceramics have very good optical permeability. But the bending resistance and fracture toughness of the ceramic are lower than those of zirconia and alumina ceramics, and the application range of the ceramic is limited to repair of veneers, inlays and the like.
In contrast, lithium disilicate glass ceramics control Li by heat treatment 2 Si 2 O 5 The precipitation amount of the crystal can reach 440MPa at most, but the mechanical property of the lithium disilicate glass ceramic is relatively weak, the brittleness and poor bending strength of the lithium disilicate glass ceramic are inherent defects of the glass ceramic, tiny cracks are easy to appear in the material after long-term cyclic loading, the cracks are increased under continuous loading, fatigue damage is generated, and the durability and mechanical strength of the material are greatly influenced. The traditional toughening mode of the ceramic mainly comprises phase change toughening, particle toughening, whisker toughening, ductile toughening and the like, and the crack tip stress of the ceramic material is reduced by means of mechanisms such as crack deflection, crack bridging, pulling-out effect, fiber debonding and the like, so that the aim of reducing crack propagation is fulfilled, and the toughness and strength of the ceramic material are improved; however, such toughening means have limitations in the preparation of lithium disilicate glass ceramics, and it is difficult to form ceramic materials having high toughness and high fracture resistance.
The hardness and wear resistance of the ceramic are far higher than those of enamel, the ceramic restoration can excessively abrade the jaw teeth, the ideal bionic ceramic teeth need to form gradient mechanical properties, the partial abrasion performance of the occlusal surface is bionic (synchronous with the speed of physiological abrasion and equivalent abrasion), and meanwhile, when the occlusal surface is subjected to excessive biting force, the natural tooth root and implant bone bonding interface is protected, and the overall strength is high and the natural tooth root is not easy to fracture. Fig. 1 is a view of the Vita Enamic glass ceramic currently in wide use, which is a typical polymer infiltrated mesh ceramic that, by infiltrating the polymer, increases the toughness of the material while reducing hardness to reduce the abrasion to the teeth of the jaw. However, as can be seen from the microstructure in the figure, the polymer is irregularly distributed in the material and cannot form gradient mechanical properties; and the discontinuous ceramic skeleton structure reduces the overall mechanical property of the material, so that the application range of the material is limited.
At the same time, the color of the natural teeth is gradient color. As can be seen from the macroscopic photograph of the glass ceramic in FIG. 1, the materials prepared by the conventional methods such as sintering method and melting method are uniform in color, and cannot fully meet the aesthetic requirements. Researches show that the light transmittance of the glass ceramic is related to phase composition, crystal number, grain size and air holes, scientific researchers have improved the glass phase composition, reduced the grain size and eliminated the influence of the air holes as much as possible by adjusting sintering process, optimizing heat treatment system and the like, but still cannot achieve gradient bionic color effect.
Chinese patent CN108618969a discloses a method for manufacturing a biomimetic ceramic dental restoration, which uses cold isostatic pressing equipment to laminate a blank block/disc. The blank is divided into three layers, wherein the upper layer is a bionic performance/color layer, the middle layer is a transition buffer layer, and the lower layer is a high-strength anti-cracking layer.
The process of the above patent is relatively complex, and the ceramic restoration body has interlayer fracture problem caused by the difference of sintering shrinkage ratios between different layers. Therefore, a need exists for a biomimetic dental ceramic with gradient mechanical properties.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide gradient bionic dental ceramics so as to solve the problems.
The technical scheme of the invention is realized as follows: a gradient biomimetic dental ceramic, comprising:
the porous ceramic frame is of a TPMS structure, and a fully-communicated netlike through hole is formed in the porous ceramic frame;
a polymer;
wherein the polymer is filled in the netlike through holes.
By adopting the technical scheme, the three-dimensional periodic minimum curved surface (Triply Periodic Minimal Surface, TPMS) is a very simple complex structure with mathematical expression, a smooth full-communicated porous structure in a three-dimensional space is periodically constructed, and the structure has the advantages of light weight, high strength, good connectivity, controllable topological structure and the like; the common TPMS structure comprises Primitive, gyroid, diamond and IW-P, a porous ceramic frame with the TPMS structure is printed by adopting a 3D printing technology, the TPMS smooth full-communication porous structure has more excellent mechanical property and permeability, a perfect combination interface can be formed between a polymer and the porous ceramic frame, when the ceramic is stressed to generate cracks, the polymer filled by the porous structure can prevent the crack from expanding, the fracture toughness of the material is greatly improved, and meanwhile, the material is prevented from being invalid due to fatigue; the porous ceramic frame of the TPMS structure is suitable for ceramics with all components, such as zirconia, alumina, ZTA, ATZ and the like.
The invention is further provided with: the porosity of the porous ceramic frame is gradually increased from top to bottom.
By adopting the technical scheme, the area with smaller stress can be reduced, the wall thickness is increased in the area with larger stress, and because the cutting end of the tooth needs higher mechanical property, the porosity of the porous ceramic frame is gradually increased from the cutting end to the neck, and Li playing a role in light transmission in the porous ceramic frame is also realized 2 Si 2 O 5 The number of crystals is gradually reduced, so that the aesthetic bionic effect of vivid and transparent cut ends and low transparent and light shielding of the neck is achieved; the stress distribution of the porous ceramic frame is continuously distributed in a gradient manner, so that the mechanical bionic requirement is met; the gradient mechanical property is achieved, and the gradient effect is achieved.
The invention is further provided with: the polymer is synthetic resin.
By adopting the technical scheme, the synthetic resin permeates into the net-shaped through holes through capillary action, so that the lithium disilicate glass ceramic can be effectively supported, and the fracture toughness of the lithium disilicate glass ceramic is effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a schematic view of the appearance and microstructure of a prior art Vita Enamid glass ceramic;
fig. 2 is a schematic diagram of a three-dimensional structure of a gradient TPMS (Gyroid) according to an embodiment of the present invention;
FIG. 3 is a side view of a gradient TPMS (Gyroid) structure according to an embodiment of the present invention;
FIG. 4 is a diagram showing the von-mis equivalent stress distribution of a gradient TPMS structure according to an embodiment of the present invention;
FIG. 5 is a schematic view of a polymer permeation TPMS structure and crack propagation according to an embodiment of the present invention;
FIG. 6 is a schematic structural view of an omnibearing planetary ball mill according to an embodiment of the present invention;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1 to 6, the present invention discloses a gradient bionic dental ceramic, comprising:
the porous ceramic frame is of a TPMS structure, and a fully-communicated netlike through hole is formed in the porous ceramic frame;
a polymer;
wherein the polymer is filled in the netlike through holes.
By adopting the technical scheme, the three-dimensional periodic minimum curved surface (Triply Periodic Minimal Surface, TPMS) is a very simple complex structure with mathematical expression, a smooth full-communicated porous structure in a three-dimensional space is periodically constructed, and the structure has the advantages of light weight, high strength, good connectivity, controllable topological structure and the like; the common TPMS structure comprises Primitive, gyroid, diamond and IW-P, a porous ceramic frame with the TPMS structure is printed by adopting a 3D printing technology, the TPMS smooth full-communication porous structure has more excellent mechanical property and permeability, a perfect combination interface can be formed between a polymer and the porous ceramic frame, when the ceramic is stressed to generate cracks, the polymer filled by the porous structure can prevent the crack from expanding, the fracture toughness of the material is greatly improved, and meanwhile, the material is prevented from being invalid due to fatigue; the porous ceramic frame of the TPMS structure is suitable for ceramics with all components, such as zirconia, alumina, ZTA, ATZ and the like.
In the embodiment of the invention, the netlike through holes are in a Gyroid porous structure.
By adopting the technical scheme, the Gyroid structure is a bionic structure, such as an interface between inorganic crystals and organic amorphous substances in echinoderm flat bone elements and a porous net surface in butterfly wing scales are similar to the Gyroid structure, and the Gyroid structure has optimal mechanical properties in four structures of TPMS, so that the strength of a porous ceramic frame is effectively improved on the premise of reducing weight, and the connectivity is better.
In the embodiment of the invention, the porosity of the porous ceramic frame is gradually increased from top to bottom.
By adopting the technical scheme, the area with smaller stress can be reduced, the wall thickness is increased in the area with larger stress, and because the cutting end of the tooth needs higher mechanical property, the porosity of the porous ceramic frame is gradually increased from the cutting end to the neck, and Li playing a role in light transmission in the porous ceramic frame is also realized 2 Si 2 O 5 The number of crystals is gradually reduced, so that the aesthetic bionic effect of vivid and transparent cut ends and low transparent and light shielding of the neck is achieved; the stress distribution of the porous ceramic frame is continuously distributed in a gradient manner, so that the mechanical bionic requirement is met; the gradient mechanical property is achieved, and the gradient effect is achieved.
In the embodiment of the invention, the porous ceramic frame is a lithium disilicate glass ceramic material, and the polymer is synthetic resin.
By adopting the technical scheme, the refractive index of the lithium disilicate is about 1.55, the refractive index of the lithium disilicate is about 1.50 after the synthetic resin is blended, the refractive index of the lithium disilicate can be further reduced after the dental filling material is added, the lithium disilicate is very similar to that of the glass ceramic, and the lithium disilicate and the synthetic resin are combinedGood aesthetic properties possessed; and lithium disilicate glass ceramic can control Li by heat treatment 2 Si 2 O 5 The precipitation amount of the crystals can control the transparency of the crystals, so that the aesthetic bionic effect of vivid and transparent cut ends and low transparent and light-shielding neck is achieved; synthetic resin permeates into the net-shaped through holes through capillary action, so that the lithium disilicate glass ceramic can be effectively supported, and the fracture toughness of the lithium disilicate glass ceramic is effectively improved.
A preparation process of gradient bionic dental ceramics comprises the following steps:
s1: preparing a pre-mixed solution by using a photo-curing resin and a dispersing agent in a certain proportion, weighing ceramic powder according to the volume ratio of powder to liquid in a certain proportion, adding a small amount of ceramic powder into the pre-mixed solution for many times, and ball-milling for 2 hours at 300r/min by using an omnibearing planetary ball mill after each addition until the ceramic powder is completely added, and ball-milling for 10 hours;
s2: adding a photoinitiator TPO, ball milling for 2 hours at 200r/min, placing the prepared slurry in a vacuum drying oven, vacuumizing for 15 minutes to fully remove bubbles, and finally obtaining ceramic slurry and storing in a dark place;
s3: adding the ceramic slurry to a 3D printer, and printing out a green part with net-shaped through holes;
s4: taking a blank and cleaning;
s5: degreasing and sintering the green body part according to a set degreasing and sintering mechanism to obtain a porous ceramic frame;
s6: mixing 40-50wt% of water, 40-50wt% of ethanol and 2-5wt% of KH570, adding 6-10wt% of acetic acid to adjust the pH to 3-4, and preparing into a silane treating agent;
s7: semi-immersing the porous ceramic frame in the prepared silane treatment agent solution, fully soaking the porous ceramic frame in the solution under the vacuum assistance of-0.1 MPa for 6 hours, taking out the porous ceramic frame, removing the redundant liquid film in the holes by a compressed air gun, and then drying the porous ceramic frame in vacuum at 60 ℃ for 6 hours;
s8: 50-70wt% of BiS-GMA and 30-50wt% of TEGDMA are mixed, and the mixture is stirred for 4-8 hours in a dark place by a stirrer at 1200rpm to obtain a resin solution;
s9: adding 0.5-1wt% of BPO or 1-2wt% of multi-initiator into the resin solution, refrigerating for 6-12 hours, and eliminating bubbles to obtain a polymer solution;
s10: semi-immersing the porous ceramic frame in polymer solution, maintaining at 40 deg.C and-0.1 Mpa under vacuum assistance for 30min, and maintaining for 10min after releasing pressure;
s11: and (3) putting the porous ceramic frame soaked by the polymer into an oven to be fired for 12-14 h at the temperature of 125-155 ℃ and slowly cooling for 1-2 h to finish the curing of the polymer.
By adopting the technical scheme, the TPMS structure can be accurately constructed by 3D printing, the printing efficiency is high, and the production efficiency is effectively improved; the silane treating agent can enable polymer solution to permeate into the porous ceramic frame to form a perfect combination interface, so that the supporting effect on the porous ceramic frame is better, when the ceramic is stressed to generate cracks, the resin filled with the porous structure can prevent the cracks from expanding, the fracture toughness of the material is greatly improved, and meanwhile, the material is prevented from being invalid due to fatigue.
In the embodiment of the invention, the silane treating agent in the step S6 is prepared by mixing 44wt% of water, 44wt% of ethanol and 3wt% of KH570, and adding 9wt% of acetic acid to adjust the pH to 3-4.
Through adopting above-mentioned technical scheme, can effectually handle porous ceramic frame to make the polymerization of polymer and porous ceramic frame inseparabler, connect more stably.
In the embodiment of the invention, the step S10 is repeated for 3 to 4 times and the liquid is added until the liquid level of the polymer solution is slightly higher than that of the porous ceramic frame, and meanwhile, the liquid level is unchanged and no bubbles are generated.
By adopting the technical scheme, the polymer can be ensured to be completely immersed into the netlike through holes of the porous ceramic frame, so that the permeation effect is better.
In the embodiment of the present invention, in step S3, the blank is printed by DLP or SLA technology.
By adopting the technical scheme, the TPMS structure can be effectively printed, and the accuracy is high.
In an embodiment of the present invention, the resin solution in the step S8 is a mixture of 60wt% of BiS-GMA and 40wt% of TEGDMA.
By adopting the technical scheme, the refractive index of the resin solution is about 1.5 and quite close to the refractive index of the porous ceramic frame to be 1.55, so that the resin can have good aesthetic property after penetrating into the porous ceramic frame and combining the porous ceramic frame and the resin to be more close to the color of natural teeth.
In an embodiment of the present invention, the omnibearing planetary ball mill includes:
the device comprises a frame 1, wherein a supporting table 2 is arranged in the frame 1, a supporting column 3 is vertically arranged on the supporting table 2, the supporting column 3 is arranged in a hollow mode, and gear patterns 30 are arranged on the outer wall of the upper end of the supporting column 3;
a ball mill 4;
a first rotation shaft 5;
the rotary disc 6 is arranged in a hollow way, a transmission cavity 8 and a filter cavity 9 are arranged in the rotary disc 6 in a separated way through an annular partition ring 7, the filter cavity 9 is arranged on the outer side of the transmission cavity 8, and the transmission cavity 8 is filled with lubricating oil;
the first gear shaft 10 is rotatably connected in the transmission cavity 8, and one end of the first gear shaft 10 is connected with the ball mill barrel 4;
the second gear shaft 11 is rotatably connected in the transmission cavity 8;
the first rotating shaft 5 penetrates through the supporting column 3 to extend out and rotate, the upper ends of the first rotating shaft 5 and the supporting column 3 extend into the transmission cavity 8, the first rotating shaft 5 is fixedly connected with the rotating disc 6, and the first gear shaft 10 is in transmission connection with the gear pattern 30 through the second gear shaft 11.
By adopting the technical scheme, when the first rotating shaft rotates, the rotating disc is driven to rotate so that the ball milling cylinder revolves along the first rotating shaft as the axis, and meanwhile, as the gear lines are fixed on the supporting columns, when the first gear shaft rotates along with the rotating disc, the first gear shaft rotates through the second gear shaft, so that the ball milling cylinder is driven to rotate on the rotating disc by taking the first gear shaft as the axis, and planetary rotation is realized; the lubricating oil which continuously circulates can radiate heat generated by the gear shaft during the meshing rotation, and impurities generated by abrasion are led into the filter cavity for filtering.
In an embodiment of the present invention, the method further includes:
a reservoir 12;
a liquid pump 13;
the filter screen 14 is annularly arranged in the filter cavity 9 to divide the filter cavity 9 into a dirty oil cavity 15 and an oil purifying cavity 16, and the oil purifying cavity 16 is positioned at the outer side of the dirty oil cavity 15;
a cooler 17;
a first self-valve 18;
a second self-operated valve 19;
the liquid outlet of the oil storage tank 12 is communicated with the dirty oil cavity 15 through the liquid drawing pump 13, the clean oil cavity 16 is communicated with the transmission cavity 8 through a first pipeline 20, the cooler 17 is arranged on the first pipeline 20, the transmission cavity 8 is communicated with the liquid inlet of the oil storage tank 12 through a first self-operated valve 18, the dirty oil cavity 15 is communicated with the liquid inlet of the oil storage tank 12 through a second pipeline 21, and a second self-operated valve 19 is arranged on the second pipeline 21.
By adopting the technical scheme, when the gears in the transmission cavity are meshed and rotated, certain abrasion occurs, so that the lubricating oil contains certain impurities; the liquid pump conveys the lubricating oil in the oil storage tank into the oil purifying cavity, impurities in the lubricating oil are filtered through the filter screen, so that the oil purifying cavity is clean lubricating oil, when the rotating disc rotates, the lubricating oil in the oil purifying cavity can quickly enter the oil purifying cavity through the filter screen under the action of centrifugal force, the filtering effect is better, the filtering speed is faster, the clean lubricating oil is cooled through the cooler and is sent into the transmission cavity, and the gears are lubricated and cooled; when the pressure is equal to or greater than a preset value, the first self-operated valve is opened and conducted, lubricating oil in the transmission cavity can enter the oil storage tank, the pressure in the transmission cavity can be kept within a certain range through the first self-operated valve, and therefore the transmission cavity can be filled with the lubricating oil, and the lubricating and cooling effects on gears are better; through the use of a period of time, the impurity of accumulation on the filter screen can increase gradually to the jam filter screen makes lubricating oil be difficult to pass through, and when the pressure in the dirty oil pocket is greater than the opening pressure value of second self-operated valve, the second self-operated valve just switches on, in will the lubricating oil in the dirty oil pocket returns the oil storage tank, thereby can effectually avoid unfiltered lubricating oil entering transmission intracavity, makes the transmission intracavity only accept clean lubricating oil.
In the embodiment of the invention, an oil seal 22 is arranged between the rotating disc 6 and the outer wall of the support column 3, and the rotating disc 6 is rotationally connected with the support column 3.
Through adopting above-mentioned technical scheme, can effectually seal lubricating oil in the transmission intracavity to make the rotation of rolling disc more light.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (1)
1. A gradient biomimetic dental ceramic, comprising:
the porous ceramic frame is of a TPMS structure, and a fully-communicated netlike through hole is formed in the porous ceramic frame;
a polymer;
wherein the polymer is filled in the netlike through holes;
the polymer is synthetic resin;
the preparation process of the gradient bionic dental ceramic comprises the following steps:
s1: preparing a pre-mixed solution by using a photo-curing resin and a dispersing agent in a certain proportion, weighing ceramic powder according to the volume ratio of powder to liquid in a certain proportion, adding a small amount of ceramic powder into the pre-mixed solution for many times, and ball-milling for 2 hours at 300r/min by using an omnibearing planetary ball mill after each addition until the ceramic powder is completely added, and ball-milling for 10 hours;
s2: adding a photoinitiator TPO, ball milling for 2 hours at 200r/min, placing the prepared slurry in a vacuum drying oven, vacuumizing for 15 minutes to fully remove bubbles, and finally obtaining ceramic slurry and storing in a dark place;
s3: adding the ceramic slurry to a 3D printer, and printing out a green part with net-shaped through holes;
s4: taking a blank and cleaning;
s5: degreasing and sintering the green body part according to a set degreasing and sintering mechanism to obtain a porous ceramic frame;
s6: mixing 40-50wt% of water, 40-50wt% of ethanol and 2-5% of KH570, adding 6-10% of acetic acid to adjust the pH to 3-4, and preparing a silane treating agent;
s7: semi-immersing the porous ceramic frame in the prepared silane treatment agent solution, fully soaking the porous ceramic frame in the solution under the vacuum assistance of-0.1 MPa for 6 hours, taking out the porous ceramic frame, removing the redundant liquid film in the holes by a compressed air gun, and then drying the porous ceramic frame in vacuum at 60 ℃ for 6 hours;
s8: 50-70wt% of BiS-GMA and 30-50wt% of TEGDMA are mixed, and the mixture is stirred for 4-8 hours in a dark place by a stirrer at 1200rpm to obtain a resin solution;
s9: adding 0.5-1wt% BPO into the resin solution, refrigerating for 6-12 hours, and eliminating bubbles to obtain a polymer solution;
s10: semi-immersing the porous ceramic frame in polymer solution, maintaining at 40 deg.C and-0.1 Mpa under vacuum assistance for 30min, and maintaining for 10min after releasing pressure;
s11: placing the porous ceramic frame after the polymer infiltration into an oven to be fired for 12-14 hours at 125-155 ℃, and slowly cooling for 1-2 hours to finish the polymer solidification;
the netlike through holes are in a Gyroid porous structure;
the porosity of the porous ceramic frame is gradually increased from top to bottom.
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| CN114835401B (en) * | 2022-04-11 | 2023-08-22 | 大连工业大学 | 3D printing preparation method of lithium disilicate glass ceramic |
| CN116041084B (en) * | 2023-01-18 | 2024-02-20 | 爱迪特（秦皇岛）科技股份有限公司 | Bionic resin-infiltrated ceramic material and preparation method thereof |
| CN116077349A (en) * | 2023-01-19 | 2023-05-09 | 爱迪特（秦皇岛）科技股份有限公司 | Gradient bionic dental restoration material and preparation method thereof |
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