CN117942267A - Method for manufacturing complete denture based on photo-curing additive of Bingham fluid material - Google Patents
Method for manufacturing complete denture based on photo-curing additive of Bingham fluid material Download PDFInfo
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- CN117942267A CN117942267A CN202410126184.XA CN202410126184A CN117942267A CN 117942267 A CN117942267 A CN 117942267A CN 202410126184 A CN202410126184 A CN 202410126184A CN 117942267 A CN117942267 A CN 117942267A
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- 238000000016 photochemical curing Methods 0.000 title claims abstract description 63
- 239000000654 additive Substances 0.000 title claims abstract description 62
- 230000000996 additive effect Effects 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000012530 fluid Substances 0.000 title claims abstract description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000002245 particle Substances 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 238000005238 degreasing Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000006254 rheological additive Substances 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 34
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000005096 rolling process Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007639 printing Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 5
- 238000007648 laser printing Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 150000003672 ureas Chemical class 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 3
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 210000000214 mouth Anatomy 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000001055 chewing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 210000004283 incisor Anatomy 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/62—Photochemical radical initiators
-
- 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
-
- 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
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- A61K6/898—Polysaccharides
Landscapes
- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Biophysics (AREA)
- Engineering & Computer Science (AREA)
- Dental Prosthetics (AREA)
Abstract
The invention relates to a method for manufacturing complete denture based on photo-curing additive of guest-to-Chinese fluid material, which comprises the following steps: the first step: preparing an organic solvent which does not participate in the photo-curing reaction, and mixing the organic solvent with photosensitive resin to obtain resin premix; and a second step of: adding a photoinitiator into the resin mixture, sequentially adding graded zirconia particles and a surfactant three times, adding a rheological additive to obtain a photo-curing additive manufacturing paste, and carrying out vacuum defoaming; and a third step of: placing the green body into additive manufacturing equipment for photo-curing forming to obtain a green body; fourth step: cleaning the green body obtained in the third step by using a flowing cleaning solution, and then soaking the cleaned green body in a flowing alkaline solution for 20-40 minutes until fine holes appear on the surface of the green body; fifth step: drying; sixth step: thermal degreasing; seventh step: sintering. The invention aims to provide a method for manufacturing a high-strength complete denture by a photocuring additive manufacturing technology based on a Bingham fluid material.
Description
Technical Field
The invention relates to an oral medical apparatus, in particular to a method for manufacturing complete denture based on photo-curing additive of guest-to-Chinese fluid materials.
Background
Dentures, also called dentures, prostheses, are a general term for a medical article that is made to replace the function of teeth in order to treat partial or complete missing teeth in the upper and lower jaws. The false tooth is divided into a movable false tooth and a fixed false tooth, wherein the movable false tooth has the advantages that a patient can take off and clean the false tooth, but has the defects of lower chewing efficiency and inconvenience in taking off and cleaning after meals; the fixed denture has the advantage of high chewing efficiency, so the application rate of the fixed denture is higher than that of the movable denture.
However, the fixed denture has certain problems: if the number of missing teeth of the patient is small, the denture can be manufactured according to the unit and then fixedly arranged in the oral cavity of the patient by using the fixing piece; however, if the number of missing teeth of the patient is large, each independent manufacturing is independently fixed in the oral cavity of the patient, which is not only troublesome, but also has poor comfort for the patient, so the method is more suitable for manufacturing complete dentures and then is fixedly arranged in the oral cavity of the patient.
Along with the development of technology, the technology of personalized additive manufacturing of complete denture by using photo-cured ceramic material is mature, and the additive manufacturing has the advantages that the complete denture matched with the material can be manufactured according to the unique oral condition of a patient, so that the patient is more comfortable when using the complete denture, and the maintenance of oral hygiene of the patient is also more convenient. However, the following problems are also involved in the additive manufacturing of complete dentures: because the thickness requirement of each tooth is different, for example, the thickness of an incisor is thinner, the thickness of a molar is thicker, the thickness of the molar can reach 2-4 mm, the degreasing difficulty degree is different due to different thicknesses, under the same degreasing environment, because the degreasing path of the tooth with larger thickness is longer, larger cracks are easy to generate in the degreasing process due to longer degreasing path, and the cracks are difficult to close in the sintering process, so that the strength of the complete denture is lower, the complete denture is easier to damage in the using process, the service life is short, and additional cost such as money, time and the like is added to a patient.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for manufacturing a high-strength complete denture by a photocuring additive manufacturing technology based on a Bingham fluid material.
The technical scheme is as follows: the invention relates to a method for manufacturing complete denture based on photo-curing additive of guest-to-Chinese fluid material, which comprises the following steps:
the first step: mixing an organic solvent which does not participate in the photo-curing reaction with photosensitive resin to obtain a resin mixture, wherein the mass of the organic solvent which does not participate in the photo-curing reaction is 5-20% of the mass of the resin mixture (mass ratio);
And a second step of: adding a photoinitiator into the resin mixture obtained in the first step, adding graded zirconia particles and a surfactant three times in sequence, adding the graded zirconia particles and the surfactant each time, then placing the mixture into a homogenizer for homogenization, placing the mixture into a roll squeezer for rolling after all the graded zirconia particles and the surfactant are added to obtain a rolling mixture, adding a rheological additive into the rolling mixture, and adjusting the rheological property of the rolling mixture to obtain a photocuring additive manufactured paste, placing the photocuring additive manufactured paste into a vacuum machine for vacuum defoamation, wherein the photocuring additive manufactured paste after the rheological property is adjusted has no fluidity under the condition of not being subjected to external force, so that the photocuring additive manufactured paste does not need to use support or less support during the subsequent photocuring additive manufacturing, and is convenient to clean, remove support and other operations after the photocuring additive manufacturing, thereby reducing the damage to green bodies;
And a third step of: placing the photocuring additive manufacturing paste subjected to vacuum defoamation in the second step into additive manufacturing equipment for photocuring forming to obtain a green body;
Fourth step: firstly, cleaning the green body obtained in the third step by using a flowing cleaning solution, and then soaking the cleaned green body in an alkaline solution for 20-40 minutes until tiny holes appear on the surface of the green body;
fifth step: drying the green body with the fine holes on the surface, which is obtained in the fourth step, to obtain a dried green body;
Sixth step: placing the dried green body obtained in the fifth step into a heating device for thermal degreasing, and initially introducing inert gas into the heating device, wherein the introducing speed of the inert gas is 0.1L/min, the temperature in the heating device is raised from room temperature to 200 ℃, and the heating rate is 1.8-2.2 ℃/min; the temperature is increased from 200 ℃ to 400 ℃ and the temperature rising rate is 0.3-0.6 ℃/min; the temperature is increased from 400 ℃ to 800 ℃ with the temperature rising rate of 0.8 to 1.5 ℃/min;
Seventh step: sintering, namely stopping introducing inert gas into the heating device at 800 ℃, and introducing air instead, wherein the air introducing speed is 0.5L/min; the temperature is increased from 800 ℃ to 1000 ℃ with the heating rate of 2-4 ℃/min; the temperature is raised from 1000 ℃ to 1350 ℃ with the temperature rising rate of 1.5-2.5 ℃/min; the temperature is raised from 1350 ℃ to 1500 ℃ with the temperature rising rate of 0.8-1.2 ℃/min; preserving heat for 0.5-4 hours at 1500 ℃; then the temperature is reduced from 1500 ℃ to 1000 ℃ with the cooling rate of 1 to 1.5 ℃/min; and finally naturally cooling the mixture in a heating device from 1000 ℃.
Further, the organic solvent which does not participate in the photo-curing reaction in the first step is one or any mixture of polyethylene glycol, N-dimethylformamide, isopropanol and N-methylpyrrolidone.
Further, the polyethylene glycol may be one or any mixture of PEG200, PEG400, PEG600, PEG 800. The polyethylene glycol can be selected from any one or any mixture of short-chain PEG200, PEG400, PEG600 and PEG800, and the short-chain polyethylene glycol can more easily permeate out of the green body along with the alkaline solution, and tiny holes are generated on the surface of the green body in the process of leaching.
Further, in the second step, the rheological additive is any one of polyvinyl alcohol, polyacrylic acid, modified urea solution and hydroxypropyl methyl cellulose, and the mass of the rheological additive is 0.1-0.5% of the total mass of the paste manufactured by the photo-curing additive.
Further, the graded zirconia particles in the second step are a mixture of zirconia particles with the particle size of 200 nanometers and zirconia particles with the particle size of 5-25 micrometers, and the mass ratio of the zirconia particles with the particle size of 200 nanometers to the zirconia particles with the particle size of 5-25 micrometers is 3:1-2:1.
Further, the zirconia particles with the particle size of 5-25 micrometers are obtained by spray granulation of zirconia powder with the original particle size of 20-50 nanometers.
Further, the solid content G of the photo-curing additive manufacturing paste obtained in the second step is more than or equal to 60vol% (volume ratio). The higher the solids content of the paste, the less photosensitive resin content of the paste, but the less suitable the paste is for photo-cured additive manufacturing.
Further, in the fourth step, the cleaning solution is a mixed solution obtained by mixing a resin monomer with low viscosity and isopropanol in a mass ratio of 1:1, and the low viscosity refers to a viscosity of less than 100mPa (millipascal). The advantage of pure isopropanol solution is high cleaning efficiency, but pure isopropanol reduces the bonding strength between green layers.
Further, in the fourth step, the alkaline solution is an ammonium nitrate solution.
Further, the pH value of the alkaline solution in the fourth step is 8.5-9.5.
Further, the alkaline solution in the fourth step is flowing at a flow rate of 0.5 m/s to 2 m/s.
Further, in the third step, the parameters of the additive manufacturing equipment are 130-150 mW of light intensity, 1000-7000 mm/s of laser printing speed, 0.01mm of printing interval and 25-50 mu m of printing layer thickness.
Advantageous effects
Compared with the prior art, the invention has the following remarkable advantages: 1. the graded zirconia particles are obtained by mixing zirconia particles with the particle size of 200 nanometers and zirconia particles with the particle size of 5-25 microns, the zirconia particles with the particle size of 5-25 microns are obtained by spray granulation of zirconia powder with the primary particle size of 20-50 nanometers, the primary particle size of 20-50 nanometers has large activity, and the zirconia particles with the particle size of 5-25 microns obtained after spray granulation have small specific surface area and are easier to disperse in the subsequent process, so the graded zirconia particles have the advantages of large activity and good dispersibility; 2. the organic solvent which does not participate in the photo-curing reaction is added into the paste with high solid content, so that the resin premix is diluted by the organic solvent which does not participate in the photo-curing reaction, the content of the photosensitive resin in unit volume is reduced, the photosensitive resin is distributed more uniformly in the paste, and a good foundation is laid for the follow-up better degreasing; 3. the green body is placed into flowing alkaline solution for soaking, the organic solvent which does not participate in the photo-curing reaction can seep out of the green body in the soaking process, fine holes are generated on the surface of the green body in the seeping process, the generated fine holes are beneficial to the discharge of organic gas in the subsequent hot degreasing process, and cracks are prevented from being generated due to the fact that the organic gas is discharged too fast in the degreasing process; 4. the flexural strength of the complete denture obtained after degreasing of the invention can reach 1050-1200 megapascals, and the national standard GB 30367-2013 of the complete denture with the total denture ceramic size of more than 800 megapascals is completely satisfied.
Drawings
FIG. 1 is a flow chart of the present invention.
FIG. 2 is a time-consuming trend of thermal degreasing and sintering according to the present invention.
Fig. 3 is a schematic representation of the change in rheological properties after addition of a rheological aid.
Fig. 4 is a partial enlarged view of a complete denture manufactured by a conventional manufacturing process.
Fig. 5 is a partial enlarged view of the complete denture manufactured by the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
The conventional method for manufacturing the complete denture comprises the following steps:
the first step: preparing a photosensitive resin monomer mixture (without other chemical solvents);
And a second step of: adding a photoinitiator into the resin mixture obtained in the first step, sequentially adding graded zirconia particles and a surfactant three times, wherein the graded zirconia particles are a mixture of zirconia particles with the particle size of 200 nanometers and zirconia particles with the particle size of 5-25 micrometers, the mass ratio of the zirconia particles with the particle size of 200 nanometers to the zirconia particles with the particle size of 5-25 micrometers is 3:1, the zirconia particles with the particle size of 5-25 micrometers are obtained by spraying and granulating zirconia powder with the original particle size of 20 nanometers-50 nanometers, homogenizing in a homogenizer after adding the graded zirconia particles and the surfactant each time, rolling the mixture after all the graded zirconia particles and the surfactant are added in a roll squeezer to obtain a rolled mixture, adding polyvinyl alcohol into the rolled mixture, adjusting the rheological property of the rolled mixture, thereby obtaining a photocuring additive paste, wherein the mass of the polyvinyl alcohol is 0.2% of the total mass of the photocuring additive paste, vacuum-producing the photocuring additive paste, and the solid content G of the photocuring additive paste is more than or equal to 60% (volume ratio) after the adding;
And a third step of: placing the photocuring additive manufacturing paste subjected to vacuum defoamation in additive manufacturing equipment for photocuring forming to obtain a green body, wherein parameters of the additive manufacturing equipment are 135mW of light intensity, 4mm/s of laser printing speed, 0.02mm of printing interval and 30 mu m of printing layer thickness;
fourth step: firstly, cleaning the green body obtained in the third step by using a flowing cleaning solution, wherein the cleaning solution is isopropanol;
Fifth step: drying the green body obtained in the fourth step to obtain a dried green body;
Sixth step: placing the dried green body obtained in the fifth step into a heating device for thermal degreasing, and initially introducing pure argon into the heating device at a rate of 0.1L/min, wherein the temperature in the heating device is raised from room temperature to 200 ℃ at a rate of 2.3 ℃/min; the temperature is increased from 200 ℃ to 400 ℃ with the temperature increasing rate of 0.33 ℃/min; the temperature is increased from 400 ℃ to 800 ℃ with the heating rate of 1.12 ℃/min;
Seventh step: sintering, namely stopping introducing pure argon into the heating device at 800 ℃, and introducing air instead, wherein the air introducing speed is 0.5L/min; the temperature is increased from 800 ℃ to 1000 ℃ with the heating rate of 2.3 ℃/min; the temperature is raised from 1000 ℃ to 1350 ℃ with the temperature raising rate of 2.2 ℃/min; the temperature is raised from 1350 ℃ to 1500 ℃ with the temperature raising rate of 0.9 ℃/min; preserving heat at 1500 ℃ for 2 hours; then the temperature is reduced from 1500 ℃ to 1000 ℃ with the cooling rate of 1.12 ℃/min; and finally naturally cooling the mixture in a heating device from 1000 ℃.
The partial enlargement of the complete denture manufactured by the conventional manufacturing process can be seen as shown in fig. 4, which causes relatively large cracks, resulting in a flexural strength of 500 mpa of the complete denture manufactured by the conventional manufacturing process.
Example 2
Referring to fig. 1-2, the method for manufacturing the complete denture based on the photo-curing additive of the Bingham fluid material comprises the following steps:
The first step: mixing PEG200 with photosensitive resin to obtain a resin mixture, wherein the mass of the PEG200 is 5-20% of the mass of the resin mixture (mass ratio);
And a second step of: adding a photoinitiator into the resin mixture obtained in the first step, sequentially adding graded zirconia particles and a surfactant three times, wherein the graded zirconia particles are a mixture of zirconia particles with the particle size of 200 nanometers and zirconia particles with the particle size of 5-25 micrometers, the mass ratio of the zirconia particles with the particle size of 200 nanometers to the zirconia particles with the particle size of 5-25 micrometers is 3:1, the zirconia particles with the particle size of 5-25 micrometers are obtained by spraying and granulating zirconia powder with the original particle size of 20 nanometers-50 nanometers, homogenizing in a homogenizer after adding the graded zirconia particles and the surfactant each time, rolling the mixture after all the graded zirconia particles and the surfactant are added in a roll squeezer to obtain a rolled mixture, adding polyvinyl alcohol into the rolled mixture, adjusting the rheological property of the rolled mixture, thereby obtaining a photocuring additive paste, wherein the mass of the polyvinyl alcohol is 0.2% of the total mass of the photocuring additive paste, vacuum-producing the photocuring additive paste, and the solid content G of the photocuring additive paste is more than or equal to 60% (volume ratio) after the adding;
And a third step of: placing the photocuring additive manufacturing paste subjected to vacuum defoamation in additive manufacturing equipment for photocuring forming to obtain a green body, wherein parameters of the additive manufacturing equipment are 135mW of light intensity, 4mm/s of laser printing speed, 0.02mm of printing interval and 30 mu m of printing layer thickness;
Fourth step: firstly, cleaning the green body obtained in the third step by using a flowing cleaning solution, wherein the cleaning solution is a mixed solution of resin monomer with viscosity less than 100 mPa and isopropanol according to a mass ratio of 1:1, then, soaking the cleaned green body in a flowing ammonium nitrate solution for 20-40 minutes, wherein the pH value of the ammonium nitrate solution is 8.5-9.5, and the flow rate of the ammonium nitrate solution is 1.2 m/s until fine holes appear on the surface of the green body;
fifth step: drying the green body with the fine holes on the surface, which is obtained in the fourth step, to obtain a dried green body;
Sixth step: placing the dried green body obtained in the fifth step into a heating device for thermal degreasing, and initially introducing pure argon into the heating device at a rate of 0.1L/min, wherein the temperature in the heating device is raised from room temperature to 200 ℃ at a rate of 2 ℃/min; the temperature is increased from 200 ℃ to 400 ℃ with the temperature increasing rate of 0.4 ℃/min; the temperature is increased from 400 ℃ to 800 ℃ with the heating rate of 1.2 ℃/min;
Seventh step: sintering, namely stopping introducing pure argon into the heating device at 800 ℃, and introducing air instead, wherein the air introducing speed is 0.5L/min; the temperature is increased from 800 ℃ to 1000 ℃ with the temperature rising rate of 3 ℃/min; the temperature is raised from 1000 ℃ to 1350 ℃ with the temperature raising rate of 2 ℃/min; the temperature is raised from 1350 ℃ to 1500 ℃ with the temperature raising rate of 1 ℃/min; preserving heat at 1500 ℃ for 2 hours; then the temperature is reduced from 1500 ℃ to 1000 ℃ with the cooling rate of 1.3 ℃/min; and finally naturally cooling the mixture in a heating device from 1000 ℃.
As shown in fig. 5, the partial enlargement of the complete denture manufactured by the present invention shows that no crack exists, and thus the flexural strength of the complete denture obtained by the present invention is 1050 mpa.
Example 3
Referring to fig. 1-2, the method for manufacturing the complete denture based on the photo-curing additive of the Bingham fluid material comprises the following steps:
The first step: mixing N, N-dimethylformamide and N-methylpyrrolidone with a photosensitive resin, wherein the total mass of the N, N-dimethylformamide and the N-methylpyrrolidone is 5% -20% of the mass of the resin mixture;
And a second step of: adding a photoinitiator into the resin mixture obtained in the first step, sequentially adding graded zirconia particles and a surfactant three times, wherein the graded zirconia particles are a mixture of zirconia particles with the particle size of 200 nanometers and zirconia particles with the particle size of 5-25 micrometers, the mass ratio of the zirconia particles with the particle size of 200 nanometers to the zirconia particles with the particle size of 5-25 micrometers is 3:1, the zirconia particles with the particle size of 5-25 micrometers are obtained by spraying and granulating zirconia powder with the original particle size of 20 nanometers-50 nanometers, homogenizing in a homogenizer after adding the graded zirconia particles and the surfactant each time, rolling the graded zirconia particles and the surfactant in a roll squeezer to obtain a rolled mixture after all the graded zirconia particles and the surfactant are added, adding a modified urea solution into the rolled mixture, adjusting the rheological property of the rolled mixture, thereby obtaining a photocuring additive manufactured paste, wherein the mass of the modified urea solution is 0.45 percent of the total mass of the photocuring additive manufactured paste, and the solid content G of the photocuring additive manufactured paste is more than or equal to 60 percent by volume percent;
And a third step of: placing the photocuring additive manufacturing paste subjected to vacuum defoamation in additive manufacturing equipment for photocuring forming to obtain a green body, wherein parameters of the additive manufacturing equipment are 145mW of light intensity, 4500mm/s of laser printing speed, 0.025mm of printing interval and 45 mu m of printing layer thickness;
Fourth step: firstly, cleaning the green body obtained in the third step by using a flowing cleaning solution, wherein the cleaning solution is a mixed solution of resin monomer with viscosity less than 100 mPa and isopropanol according to a mass ratio of 1:1, and then, soaking the cleaned green body in a flowing ammonium nitrate solution for 20-40 minutes, wherein the pH value of the ammonium nitrate solution is 8.5-9.5, and the flow rate of the ammonium nitrate solution is 0.9 m/s until fine holes appear on the surface of the green body;
fifth step: drying the green body with the fine holes on the surface, which is obtained in the fourth step, to obtain a dried green body;
sixth step: placing the dried green body obtained in the fifth step into a heating device for thermal degreasing, and initially introducing inert gas into the heating device, wherein the introducing speed of the inert gas is 0.1L/min, and the temperature in the heating device is raised from room temperature to 200 ℃ at a heating rate of 1.85 ℃/min; the temperature is increased from 200 ℃ to 400 ℃ with the temperature increasing rate of 0.35 ℃/min; the temperature is increased from 400 ℃ to 800 ℃ with the temperature increasing rate of 0.9 ℃/min;
Seventh step: sintering, namely stopping introducing inert gas into the heating device at 800 ℃, and introducing air instead, wherein the air introducing speed is 0.5L/min; the temperature is increased from 800 ℃ to 1000 ℃ with the heating rate of 2.5 ℃/min; the temperature is raised from 1000 ℃ to 1350 ℃ with the temperature raising rate of 1.7 ℃/min; the temperature is raised from 1350 ℃ to 1500 ℃ with the temperature raising rate of 0.9 ℃/min; preserving heat at 1500 ℃ for 3.5 hours; then the temperature is reduced from 1500 ℃ to 1000 ℃ with the cooling rate of 1.1 ℃/min; and finally naturally cooling the mixture in a heating device from 1000 ℃.
As shown in fig. 5, the complete denture manufactured by the present invention has no cracks after the partial enlargement, and thus the flexural strength of the complete denture obtained by the present invention is 1150 mpa.
The lower curve in fig. 3 shows the rheological properties before the addition of the rheological additive, and the upper curve shows the rheological properties after the addition of the rheological additive, and it can be seen from fig. 3 that after the addition of the rheological additive, the required shear stress is greater at the same shear rate and the flowability resistance is better than that without the addition of the rheological additive.
Claims (10)
1.A method for manufacturing complete denture based on photo-curing additive of guest-to-Chinese fluid material comprises the following steps:
the first step: mixing an organic solvent which does not participate in the photo-curing reaction with photosensitive resin to obtain a resin mixture, wherein the mass of the organic solvent which does not participate in the photo-curing reaction is 5% -20% of the mass of the resin mixture;
And a second step of: adding a photoinitiator into the resin mixture obtained in the first step, sequentially adding graded zirconia particles and a surfactant for three times, homogenizing in a homogenizer after adding the graded zirconia particles and the surfactant each time, putting the graded zirconia particles and the surfactant into a roll squeezer for rolling after all the graded zirconia particles and the surfactant are added to obtain a rolling mixture, adding a rheological additive into the rolling mixture, and adjusting the rheological property of the rolling mixture to obtain a photocuring additive manufactured paste, and putting the photocuring additive manufactured paste into a vacuum machine for vacuum defoaming;
And a third step of: placing the photocuring additive manufacturing paste subjected to vacuum defoamation in the second step into additive manufacturing equipment for photocuring forming to obtain a green body;
Fourth step: firstly, cleaning the green body obtained in the third step by using a flowing cleaning solution, and then, soaking the cleaned green body in a flowing alkaline solution for 20-40 minutes until tiny holes appear on the surface of the green body;
fifth step: drying the green body with the fine holes on the surface, which is obtained in the fourth step, to obtain a dried green body;
Sixth step: placing the dried green body obtained in the fifth step into a heating device for thermal degreasing, and initially introducing inert gas into the heating device, wherein the introducing speed of the inert gas is 0.1L/min, the temperature in the heating device is raised to 200 ℃ from room temperature, and the heating rate is 1.8-2.2 ℃/min; the temperature is increased from 200 ℃ to 400 ℃ and the temperature rising rate is 0.3-0.6 ℃/min; the temperature is increased from 400 ℃ to 800 ℃ with the temperature rising rate of 0.8 to 1.5 ℃/min;
Seventh step: sintering, namely stopping introducing inert gas into the heating device at 800 ℃, and introducing air instead, wherein the air introducing speed is 0.5L/min; the temperature is increased from 800 ℃ to 1000 ℃ with the heating rate of 2-4 ℃/min; the temperature is raised from 1000 ℃ to 1350 ℃ with the temperature rising rate of 1.5-2.5 ℃/min; the temperature is raised from 1350 ℃ to 1500 ℃ with the temperature rising rate of 0.8-1.2 ℃/min; preserving heat for 0.5-4 hours at 1500 ℃; then the temperature is reduced from 1500 ℃ to 1000 ℃ with the cooling rate of 1 to 1.5 ℃/min; and finally naturally cooling the mixture in a heating device from 1000 ℃.
2. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 1, wherein the method comprises the following steps of: the organic solvent which does not participate in the photo-curing reaction in the first step is one or any mixture of polyethylene glycol, N-dimethylformamide, isopropanol and N-methylpyrrolidone.
3. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 2, wherein the method comprises the following steps of: the polyethylene glycol can be one or any mixture of PEG200, PEG400, PEG600 and PEG 800.
4. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 1, wherein the method comprises the following steps of: in the second step, the rheological additive is any one of polyvinyl alcohol, polyacrylic acid, modified urea solution and hydroxypropyl methyl cellulose, and the mass of the rheological additive is 0.1-0.5% of the total mass of the paste manufactured by the photo-curing additive.
5. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 1, wherein the method comprises the following steps of: in the second step, the graded zirconia particles are a mixture of zirconia particles with the particle size of 200 nanometers and zirconia particles with the particle size of 5-25 micrometers, and the mass ratio of the zirconia particles with the particle size of 200 nanometers to the zirconia particles with the particle size of 5-25 micrometers is 3:1-2:1.
6. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 5, wherein the method comprises the following steps of: the zirconia particles with the particle size of 5-25 microns are obtained by spray granulation of zirconia powder with the original particle size of 20-50 nanometers.
7. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 1, wherein the method comprises the following steps of: in the fourth step, the cleaning solution is a mixed solution of a low-viscosity resin monomer and isopropanol in a mass ratio of 1:1, wherein the low-viscosity is a mixed solution with a viscosity of less than 100 mPa.
8. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 1, wherein the method comprises the following steps of: in the fourth step, the alkaline solution is ammonium nitrate solution, and the flow rate is 0.5-2 m/s.
9. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 1, wherein the method comprises the following steps of: and in the fourth step, the pH value of the alkaline solution is 8.5-9.5.
10. The method for manufacturing the complete denture based on the photo-curing additive of the guest-to-Chinese fluid material according to claim 1, wherein the method comprises the following steps of: the parameters of the additive manufacturing equipment in the third step are 130-150 mW of light intensity, 1000-7000 mm/s of laser printing speed, 0.01-0.03 mm of printing interval and 25-50 mu m of printing layer thickness.
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