CN115944540A - Dental machinable composite material and preparation method and application thereof - Google Patents
Dental machinable composite material and preparation method and application thereof Download PDFInfo
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- CN115944540A CN115944540A CN202211589594.5A CN202211589594A CN115944540A CN 115944540 A CN115944540 A CN 115944540A CN 202211589594 A CN202211589594 A CN 202211589594A CN 115944540 A CN115944540 A CN 115944540A
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000005470 impregnation Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000010453 quartz Substances 0.000 claims description 17
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052863 mullite Inorganic materials 0.000 claims description 16
- 238000001723 curing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 claims description 11
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 9
- 238000002444 silanisation Methods 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- 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 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000010433 feldspar Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical group O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001029 thermal curing Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 3
- 239000011664 nicotinic acid Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 229910010293 ceramic material Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 239000000805 composite resin Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000006884 silylation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000012520 frozen sample Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 210000005239 tubule Anatomy 0.000 description 3
- 229940115440 aluminum sodium silicate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011351 dental ceramic Substances 0.000 description 2
- 210000004268 dentin Anatomy 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000006112 glass ceramic composition Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000429 sodium aluminium silicate Substances 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UUEYEUDSRFNIQJ-UHFFFAOYSA-N CCOC(N)=O.CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O Chemical compound CCOC(N)=O.CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O UUEYEUDSRFNIQJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- 239000011858 nanopowder Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Dental Preparations (AREA)
Abstract
The invention provides a dental machinable composite material, a preparation method and application thereof. The porous prefabricated body has an ordered sheet layered structure, the structure not only improves the mechanical property, but also simulates the structure of the natural tooth root canal to a certain extent, and has certain bionic significance. Compared with single inorganic powder particles, the addition of the fibers in the porous preform not only reduces the defects generated by a lamellar structure, but also prevents the occurrence of cracks to a certain extent. The composite material has the advantages of both inorganic material and resin material, comprehensive mechanical performance and aesthetic performance, high light transmission, high fracture toughness and high bending strength.
Description
Technical Field
The invention belongs to the technical field of dental repair materials, and particularly relates to a dental machinable composite material and a preparation method and application thereof.
Background
With the development of the times and the progress of science and technology, compared with the traditional preparation method of the oral repair material, a computer-aided design/computer-aided manufacturing (CAD/CAM) method is widely applied to the dental repair field. Particularly, the chair-side CAD/CAM repair technology can provide personalized repair bodies according to different symptoms of patients, and meets the requirements of the patients to a great extent. In addition, the CAD/CAM repair technology beside the chair is time-saving, rapid, accurate and reliable, has visible effect, brings great convenience to oral patients and dentists, and is accepted more and more.
In contrast, the demand for machinable dental restorative materials compatible with the CAD/CAM technology systems is also increasing. Dental restorative materials can be divided into metal materials, ceramic materials, resin materials, composite materials and the like according to the composition. The metal material has better mechanical property, but has poorer biocompatibility and aesthetic property. The ceramic material comprises an all-ceramic material, a feldspar ceramic material, a glass ceramic material and the like, wherein the all-ceramic material has excellent biocompatibility, aesthetic property and mechanical property, but the hardness and modulus of the ceramic are far higher than those of a normal tooth, so that the jaw tooth is abraded, and the use of the all-ceramic material in real life is limited by a complicated preparation process. Feldspar ceramic material and glass ceramic material have good aesthetic effect, but the mechanical property needs to be improved. The resin material has low cost and simple preparation process, but has lower mechanical property, and is mainly used for temporary restorations.
The machinable composite material generally refers to resin-based composite materials, and can be divided into two types according to different preparation processes, wherein one type is that resin is used as a matrix, inorganic particles are mixed and dispersed in the resin matrix to obtain composite resin, and then the composite resin is cured and formed at high temperature and high pressure; the other type is that the porous ceramic is taken as a matrix, and resin is infiltrated into the porous ceramic. CN112494341A discloses a dental restoration composition and a preparation method thereof, wherein raw materials such as barium glass powder, nano powder, chopped fiber, glass flake and resin are ball-milled into precursor powder, and the precursor powder is subjected to dry pressing, heating and pressurizing treatment to obtain a composite material suitable for a dental chair CAD/CAM system. However, this method not only has the problem of uneven dispersion of the powder, but also increases the difficulty of practical production due to high-temperature and high-pressure treatment. CN106007802A discloses a resin-permeable ceramic composite material and a preparation method thereof, wherein a porous ceramic preform is obtained by dry pressing, isostatic pressing and sintering, and then the porous prepolymer is placed in a mixed resin liquid for vacuum impregnation and thermosetting to obtain the resin-permeable ceramic composite material. However, the method cannot ensure the uniformity of the pores in the porous ceramic material, and part of the pores may not be communicated after sintering, so that the porous ceramic material cannot be completely impregnated by resin.
The freeze casting method is a method for effectively preparing the oriented ordered porous material by using ice crystals as templates and realizing controllable growth of the ice crystals by utilizing temperature gradient, and has the advantages of small environmental pollution, simple process, controllable porosity, small processing shrinkage rate and the like. The ordered porous sheet laminated structure constructed by the freeze casting method not only simulates the arrangement structure of dentinal tubules, but also has anisotropy. The preparation method is more economical, effective and simple than the preparation method of the machinable composite material obtained by curing the composite resin at high temperature and high pressure or sintering the impregnated resin by dry pressing.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a dental machinable composite material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a dental machinable composite material comprising two continuous phases of a resin matrix and a porous preform, wherein the porous preform is prepared from raw materials including fibers, inorganic powder particles and additives.
The composite material comprises two continuous phases of a resin matrix and a porous prefabricated body, wherein the structure of the porous prefabricated body is an ordered sheet layered structure, the structure not only improves the mechanical property, but also simulates the structure of a natural tooth root canal to a certain extent, and the composite material has certain bionic significance. Compared with single inorganic powder particles, the addition of the fibers in the porous preform not only reduces the defects generated by a lamellar structure, but also prevents the occurrence of cracks to a certain extent. The composite material has the advantages of both inorganic material and resin material, comprehensive mechanical performance and aesthetic performance, high light transmittance, high fracture toughness and high bending strength.
Preferably, the material of the resin matrix comprises any one of bisphenol A-glycidyl dimethacrylate, ethoxylated bisphenol A dimethacrylate, hydroxyethyl methacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate or bisphenol A epoxy resin or a combination of at least two of the same; further preferred is a combination of urethane dimethacrylate and bisphenol a epoxy resin.
The invention creatively discovers that the urethane dimethacrylate and the bisphenol A epoxy resin can positively influence each other, and the combined use of the urethane dimethacrylate and the bisphenol A epoxy resin can improve the mechanical property and the light transmittance of the composite material.
Preferably, the porosity of the porous preform is 10-50%, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc., and other specific values within the above numerical ranges can be selected, which is not described herein again; more preferably 20 to 30%.
The porosity of the porous preform is controlled to be 10-50%, which is beneficial to the permeation of the resin impregnation liquid to form a continuous phase.
Preferably, the mass ratio of the resin matrix to the porous preform is (1-5): 1, e.g. 1.
When the mass ratio of the resin matrix to the porous preform is (1-5): 1, the mechanical properties and light transmittance of the composite material are optimized.
Preferably, the inorganic powder particles comprise any one or a combination of at least two of alumina, zirconia, calcium hydroxy phosphate, feldspar porcelain powder, barium glass powder, quartz glass powder or sodium aluminum silicate; further preferred is a combination of alumina and sodium aluminum silicate.
The invention creatively discovers that the aluminum oxide and the sodium aluminum silicate have potential interaction, can positively influence each other, and have certain synergistic effect on improving the mechanical property and the light transmittance of the composite material.
Preferably, the fibers comprise any one or a combination of at least two of glass fibers, quartz fibers, or mullite fibers; further preferred is a combination of quartz fibers and mullite fibers.
The invention creatively discovers that the combination of the quartz fiber and the mullite fiber has potential interaction, can further reduce the defects generated by the lamellar structure, prevents cracks from occurring and improves the mechanical property of the product.
Preferably, the mass ratio of the inorganic powder particles to the fibers is (1-5): 1, for example, 1.
Preferably, the additives include a binder and a dispersant.
Preferably, the binder comprises any one of or a combination of at least two of sodium carboxymethylcellulose, polyvinyl alcohol or chitosan.
Preferably, the dispersant comprises any one of citric acid, acetic acid or Dolapix CE 64 or a combination of at least two thereof.
Preferably, the mass of the binder is 1-5% of the mass of the porous preform, such as 1%, 2%, 3%, 4%, 5%, etc., and other specific values within the above numerical ranges can be selected, which is not repeated herein.
Preferably, the mass of the dispersant is 1-10% of the mass of the porous preform, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., and other specific values within the above numerical ranges can be selected, which is not described in detail herein.
In a second aspect, the present invention provides a method of preparing a dental machinable composite material according to the first aspect, the method comprising:
(1) Dispersing fibers, inorganic powder particles and an additive in a solvent to obtain slurry;
(2) After the slurry is directionally frozen, carrying out freeze drying and sintering treatment to obtain a porous prefabricated body;
(3) Silanizing the porous prefabricated body and drying;
(4) And impregnating the porous prefabricated body after the silanization treatment by using a resin impregnating solution, and performing thermocuring to obtain the dental machinable composite material.
The preparation method of the dental machinable composite material has the advantages of simple process, easy operation and good repeatability.
Preferably, the solvent is water and/or tert-butanol.
Preferably, the dispersion process of the inorganic powder particles, the fibers and the additives in the solvent is ball milling, the grinding material for ball milling is zirconia balls, the ball-to-material ratio is (10-20): 1, and the time is 2-14h, wherein the specific points in (10-20) can be selected from 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and the like, the ball milling time can be selected from 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h and the like, and other specific points in the above numerical value ranges can be selected, and are not described any more.
Preferably, the mass ratio of the total mass of the fiber and the inorganic powder particles to the solvent is (1-15): 20, wherein the specific points in (1-15) can be selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and the like.
Preferably, the particle size of the inorganic powder particles is 0.01-20 μm, such as 0.01 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, etc., and other specific values within the above ranges can be selected, which are not further described herein; further preferably 0.01 to 10 μm.
Preferably, the length of the fiber is 0.1-5mm, such as 0.1mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, and the like, and other specific points within the above numerical ranges can be selected, which is not described in detail herein; more preferably 1 to 3mm.
Preferably, the diameter of the fiber is 0.1-20 μm, such as 0.1 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, etc., and other specific points within the above numerical ranges can be selected, which is not described in detail herein; more preferably 0.5 to 10 μm,
preferably, the ball milling rotation speed is 300-600rpm, such as 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, and the like, and other specific values within the above numerical ranges can be selected, which is not described herein again.
Preferably, the temperature of the directional freezing is-180 to-50 ℃, the time is 5 to 10min, the temperature of the directional freezing can be selected from-180 ℃, -170 ℃, -160 ℃, -150 ℃, -140 ℃, -130 ℃, -120 ℃, -110 ℃, -100 ℃, -90 ℃, -80 ℃, -70 ℃, -60 ℃, -50 ℃ and the like, the time of the directional freezing can be selected from 5min, 6min, 7min, 8min, 9min, 10min and the like, and other specific values in the numerical value ranges can be selected, and are not described in detail.
Preferably, the temperature of the freeze drying is-60 to-40 ℃, the time is 12 to 24 hours, the temperature of the freeze drying can be selected from-60 ℃, 55 ℃, 50 ℃, 45 ℃, 40 ℃ and the like, the time of the freeze drying can be selected from 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours and the like, and other specific values in the numerical value ranges can be selected, so that the detailed description is omitted.
Preferably, the freeze-drying is performed under a vacuum environment.
Preferably, the temperature rise rate of the sintering treatment is 5-20 ℃/min, such as 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min, 15 ℃/min, 16 ℃/min, 17 ℃/min, 18 ℃/min, 19 ℃/min, 20 ℃/min, and the like, and other specific point values within the above numerical range can be selected, and are not repeated herein.
Preferably, the temperature of the sintering treatment is 500-800 ℃, the time is 10min-2h, the temperature of the sintering treatment can be 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ and the like, the time of the sintering treatment can be 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min and the like, and other specific point values in the numerical range can be selected, so that the description is omitted.
The ordered porous sheet laminated structure constructed by the freeze casting method has the advantages of small environmental pollution, simple process, controllable porosity, small processing shrinkage and the like. Not only simulates the arrangement structure of dentin tubules, but also has anisotropy. Is a more economical, effective and simple preparation method.
Preferably, the silanization treatment refers to impregnation of the porous preform with a silane coupling agent.
The inorganic component is subjected to surface silanization treatment, so that the adhesion between an organic phase and an inorganic phase can be effectively realized, and the influence of an interface effect is reduced.
Preferably, the impregnation includes vacuum impregnation and atmospheric impregnation.
Preferably, the silane coupling agent comprises any one of gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-aminopropyltrimethoxysilane or a combination of at least two thereof;
preferably, the silylation temperature is 10-35 ℃ and the silylation time is 3-6h, the silylation temperature can be selected from 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃ and the like, the silylation time can be selected from 3h, 4h, 5h, 6h and the like, and other specific values in the numerical ranges can be selected, which is not described in detail herein.
Preferably, the drying temperature is 60-80 ℃, the drying time is 10-20h, the drying temperature can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and the like, the drying time can be 10h, 12h, 14h, 16h, 18h, 20h and the like, and other specific values in the numerical ranges can be selected, which is not described in detail herein.
Preferably, the resin-impregnating liquid comprises a resin and a curing agent.
Preferably, the curing agent comprises any one of or a combination of at least two of benzoyl peroxide, azobisisobutyronitrile, tert-butyl peroxyacetate or 2-ethyl-4-methylimidazole.
Preferably, the preparation method of the infiltration solution is to mix the resin and the curing agent at 55-65 ℃, for example, 55 ℃, 57 ℃, 59 ℃, 61 ℃, 63 ℃, 65 ℃ and the like, and other specific values within the above numerical value ranges can be selected, which is not described herein again.
Preferably, the curing agent is 0.1-2% of the total mass of the resin, such as 0.1%, 0.3%, 0.5%, 0.7%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, etc., and other specific values within the above numerical ranges can be selected, which is not described herein again.
Preferably, the impregnation temperature is 55-65 ℃ and the impregnation time is 1-2h; the impregnation temperature can be 55 ℃, 57 ℃, 59 ℃, 61 ℃, 63 ℃ and 65 ℃, the impregnation time can be 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h and the like, and other specific point values in the numerical value ranges can be selected, which is not described in detail herein.
Preferably, the impregnation is performed under vacuum.
Preferably, the thermosetting temperature is 80-120 ℃, the time is 6-20h, the thermosetting temperature can be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ and the like, the thermosetting time can be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h and the like, and other specific point values in the numerical range can be selected, which is not described in detail herein.
In a third aspect, the present invention provides a use of a dental machinable composite material according to the first aspect in the manufacture of a dental restorative material.
Compared with the prior art, the invention has the following beneficial effects:
the composite material comprises two continuous phases of a resin matrix and a porous prefabricated body, wherein the structure of the porous prefabricated body is an ordered sheet layered structure, the structure not only improves the mechanical property, but also simulates the structure of a natural tooth root canal to a certain extent, and the composite material has certain bionic significance. Compared with single inorganic powder particles, the addition of the fibers in the porous preform not only reduces the defects generated by a lamellar structure, but also prevents the occurrence of cracks to a certain extent. The composite material has the advantages of both inorganic material and resin material, comprehensive mechanical performance and aesthetic performance, high light transmittance, high fracture toughness and high bending strength.
The preparation method of the dental machinable composite material has simple process, easy operation and good repeatability. The ordered porous sheet laminated structure constructed by the freeze casting method has the advantages of small environmental pollution, simple process, controllable porosity, small processing shrinkage rate and the like. Not only simulates the arrangement structure of dentin tubules, but also has anisotropy.
Detailed Description
In order to further illustrate the technical means and effects of the present invention, the technical solutions of the present invention are further described below with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
The following examples, comparative examples, application examples and comparative application examples relate to products in which the source of the functional ingredients are as follows (only the functional ingredients are shown, and the necessary auxiliary ingredients contained in other commercially available raw materials are not described again):
urethane dimethacrylate was purchased from Shanghai Aladdin Biotech Co., ltd under the trade name of diurethane dimethacrylate;
bisphenol a epoxy resin is available from Sigma under the trade name bisphenol a epoxy resin;
bisphenol a-glycidyl dimethacrylate was derived from a product sold under the trade name glycidyl dimethacrylate available from shanghai alading biochemical science and technology ltd;
the ethoxylated bisphenol a dimethacrylate was derived from a product sold under the trade name ethoxylated bisphenol a dimethacrylate available from shanghai bi medical science and technology gmbh;
hydroxyethyl methacrylate is derived from a product sold under the trade name hydroxyethyl methacrylate from Shanghai Aladdin Biotechnology Ltd;
the triethylene glycol dimethacrylate is derived from a product sold under the trade name triethylene glycol dimethacrylate from Shanghai Allantin Biotechnology GmbH;
the glass fiber is from a product with a trade name of glass fiber purchased from Shanghai spectral vibration Biotechnology Limited;
the quartz fiber is obtained from a product sold under the trade name quartz fiber by Shanghai Aladdin Biotechnology GmbH;
the mullite fiber is from a product which is purchased from Shanghai Aladdin Biotechnology Co., ltd and is named as the mullite fiber;
the sodium carboxymethylcellulose is obtained from a product which is purchased from Shanghai Aladdin Biotechnology GmbH and is sold under the trade name of sodium carboxymethylcellulose;
the chitosan is a product which is purchased from Shanghai Aladdin Biotechnology GmbH and is sold as chitosan;
the polyvinyl alcohol is derived from a product sold under the trade name polyvinyl alcohol from the biochemical company of Meclin, shanghai;
dolapix CE 64 is derived from a product sold under the trade name Dolapix CE 64 dispersant from crown electromechanical devices, limited, of shanghai.
Example 1
This example provides a dental machinable composite material prepared by the following steps:
(1) Preparing slurry: 20g of deionized water, 5wt% of acetic acid, 5.5g of sodium aluminum silicate, 5.5g of alumina, 1.5g of quartz fiber and 1.5g of mullite fiber are sequentially added into a ball ink tank, and after ball milling is carried out at the rotating speed of 600rpm (ball-to-material ratio is 20) for 12 hours, polyvinyl alcohol (2 wt%) is added, then the rotating speed is reduced, and ball milling is carried out at the rotating speed of 300rpm for 2 hours to obtain slurry.
(2) Preparation of porous preform: injecting the slurry into a mold with a copper bar at the bottom, placing into a container filled with liquid nitrogen, directionally freezing at-80 deg.C for 10min, placing the frozen sample in a freeze drier, and drying at-55 deg.C under vacuum for 24h to obtain porous skeleton. Heating to 400 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, then heating to 800 ℃, and preserving heat for 10min to obtain the porous preform.
(3) Silanization treatment of porous preforms: mixing ethanol, deionized water and gamma-methacryloxypropyltrimethoxysilane according to a volume ratio of 80. And (3) placing the porous preform into the mixed solution, carrying out vacuum impregnation for 1h, keeping other conditions unchanged, carrying out normal pressure impregnation for 4h, and then drying in a vacuum oven at 60 ℃ for 15h.
(4) Resin penetration porous prepolymer: preparing urethane dimethacrylate and bisphenol A epoxy resin according to a mass ratio of 1. And (4) immersing the porous preform treated in the step (3) in a resin impregnation liquid, impregnating for 3 hours in a vacuum environment, curing for 6 hours at 80 ℃, and curing for 6 hours at 120 ℃ to obtain the dental machinable composite material.
Example 2
This example provides a dental machinable composite material prepared by the following steps:
(1) Preparing slurry: 20g of deionized water, 2wt% of citric acid, 5.8g of zirconia, 5.8g of calcium hydroxy phosphate, 1.2g of quartz fiber and 1.2g of mullite fiber are sequentially added into a ball ink tank, and after ball milling is carried out at the rotating speed of 600rpm (ball-to-material ratio is 20) for 12 hours, sodium carboxymethylcellulose (1 wt%) is added, then the rotating speed is reduced, and ball milling is carried out at the rotating speed of 300rpm for 2 hours to obtain slurry.
(2) Preparation of porous preforms: injecting the slurry into a mold with a copper bar at the bottom, placing into a container filled with liquid nitrogen, directionally freezing at-80 deg.C for 10min, placing the frozen sample in a freeze drier, and drying at-55 deg.C for 20h to obtain porous skeleton. Heating to 400 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, then heating to 700 ℃, and preserving heat for 30min to obtain the porous preform.
(3) Silanization treatment of porous preforms: mixing ethanol, deionized water and gamma-methacryloxypropyltrimethoxysilane according to a volume ratio of 80. And (3) placing the porous preform into the mixed solution, carrying out vacuum impregnation for 1h, keeping other conditions unchanged, carrying out normal pressure impregnation for 4h, and then drying in a vacuum oven at 60 ℃ for 15h.
(4) Resin penetration porous prepolymer: preparing bisphenol A-glycidyl dimethacrylate and ethoxylated bisphenol A dimethacrylate according to a mass ratio of 1. And (4) immersing the porous preform treated in the step (3) in a resin impregnation liquid, impregnating for 3 hours in a vacuum environment, curing for 6 hours at 80 ℃, and curing for 6 hours at 120 ℃ to obtain the dental machinable composite material.
Example 3
This example provides a dental machinable composite material prepared by the following steps:
(1) Preparation of slurry: 20g of deionized water, 8wt% of Dolapix CE 64, 4g of feldspar porcelain powder, 4g of barium glass powder, 3g of quartz fiber and 3g of glass fiber are sequentially added into a ball ink tank, and after ball milling is carried out at the rotating speed of 600rpm (ball-to-material ratio is 20).
(2) Preparation of porous preform: injecting the slurry into a mold with a copper bar at the bottom, placing into a container filled with liquid nitrogen, directionally freezing at-80 deg.C for 10min, placing the frozen sample in a freeze drier, and drying at-55 deg.C under vacuum for 20h to obtain porous skeleton. Heating to 400 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, then heating to 600 ℃, and preserving heat for 1h to obtain the porous preform.
(3) Silanization treatment of porous preforms: mixing ethanol, deionized water and gamma-methacryloxypropyltrimethoxysilane according to a volume ratio of 80. And (3) placing the porous preform into the mixed solution, carrying out vacuum impregnation for 1h, keeping other conditions unchanged, carrying out normal-pressure impregnation for 4h, taking out, and drying in a vacuum oven at 60 ℃ for 15h.
(4) Resin penetration porous prepolymer: preparing hydroxyethyl methacrylate and triethylene glycol dimethacrylate according to a mass ratio of 1. And (4) immersing the porous prefabricated body treated in the step (3) in a resin impregnation liquid, impregnating for 3 hours in a vacuum environment, and curing for 12 hours at 120 ℃ to obtain the dental machinable composite material.
Example 4
This example provides a dental machinable composite which differs from example 1 only in that sodium aluminium silicate is not present, its mass is distributed to the mass of alumina, and the other components and contents remain unchanged. The preparation method is as in example 1.
Example 5
This example provides a dental machinable composite material which differs from example 1 only in that it does not contain alumina, its mass is distributed to the mass of the sodium aluminium silicate, and the other components and contents remain unchanged. The preparation method is as in example 1.
Example 6
This example provides a dental machinable composite which differs from example 1 only in that the quartz fiber is not present, the mass is distributed to the mass of the mullite fiber, and the other components and contents remain unchanged. The preparation method is as in example 1.
Example 7
This example provides a dental machinable composite which differs from example 1 only in that the mullite fiber is absent and its mass is distributed to the mass of the quartz fiber, the other components and contents remaining unchanged. The preparation method is as in example 1.
Example 8
This example provides a dental machinable composite which differs from example 1 only in that it does not contain urethane dimethacrylate, its mass is distributed to the mass of bisphenol a epoxy resin, and the other ingredients and contents remain unchanged. The preparation method is referred to example 1.
Example 9
This example provides a dental machinable composite which differs from example 1 only in that the bisphenol a epoxy resin is not included, the mass thereof is distributed to the mass of the urethane dimethacrylate, and the other components and contents are kept unchanged. The preparation method is as in example 1.
Example 10
This example provides a dental machinable composite which differs from example 1 only in that 5.5g of sodium aluminum silicate, 5.5g of alumina, 1.5g of quartz fiber, 1.5g of mullite fiber were replaced by 3g of sodium aluminum silicate, 3g of alumina, 4g of quartz fiber, 4g of mullite fiber, and the other components and contents were maintained. The preparation method is as in example 1.
Example 11
This example provides a dental machinable composite material which differs from example 1 only in that 5.5g of sodium aluminum silicate, 5.5g of alumina, 1.5g of quartz fiber, 1.5g of mullite fiber are replaced with 6g of sodium aluminum silicate, 6g of alumina, 1g of quartz fiber, 1g of mullite fiber, and the other components and contents are kept unchanged. The preparation method is as in example 1.
Example 12
This example provides a dental machinable composite material, which differs from example 1 only in that the porous preform is prepared by placing a slurry in a steel mold, pressing at 4MPa for 2min, raising the temperature to 400 ℃ at a rate of 10 ℃/min after molding, holding the temperature for 1h, then raising the temperature to 800 ℃ and holding the temperature for 10min to obtain a porous preform. The composition, content and other preparation methods of the composite material remain unchanged.
Test example 1
The test method comprises the following steps: the machinable composite was prepared as 35mm x 4mm x 3mm spline chamfer buffed test flexural strength per 10 specimens per group according to the criteria of GB 30367-2013 dental ceramic materials. The cuttable composites were prepared as 44mm x 4mm x 3mm specimens, polished and v-grooved, and tested for fracture toughness, 7 specimens per group. Hardness was measured by a Vickers hardness tester (2mm 2mm samples with smooth surfaces) and light transmittance was measured by a haze meter (round samples 25mm in diameter and 1mm in thickness).
TABLE 1
As can be seen from the data in Table 1: the dental machinable composite material has excellent mechanical property and light transmittance, and accords with the standard of GB 30367-2013 dental ceramic materials, a synergistic effect exists between the urethane dimethacrylate and the bisphenol A epoxy resin in the resin material in the aspect of improving the mechanical property and the light transmittance of the composite material, a synergistic effect exists between the alumina and the sodium aluminum silicate in the inorganic powder particles in the aspect of improving the mechanical property and the light transmittance of the composite material, and a synergistic effect exists between the mullite fiber and the quartz fiber in the aspect of improving the mechanical property of the composite material. In addition, the ordered lamellar structure obtained by directional freezing by adopting a freeze-drying method has certain enhancement effect on the mechanical property and the aesthetic property of the composite material.
The applicant states that the present invention is illustrated by the above examples of dental machinable composite material of the present invention and its preparation method and application, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. A dental machinable composite material comprising two continuous phases of a resin matrix and a porous preform, wherein the porous preform is prepared from raw materials including a fiber, inorganic powder particles and an additive.
2. The dental machinable composite of claim 1, wherein the material of the resin matrix comprises any one or a combination of at least two of bisphenol a-glycidyl dimethacrylate, ethoxylated bisphenol a dimethacrylate, hydroxyethyl methacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate, or bisphenol a epoxy resin; preferably a combination of urethane dimethacrylate and bisphenol a epoxy resin.
3. Dental machinable composite material according to claim 1 or 2, characterized in that the porosity of the porous preform is 10-50%, preferably 20-30%;
preferably, the mass ratio of the resin matrix to the porous preform is (1-5): 1;
preferably, the inorganic powder particles comprise any one or a combination of at least two of alumina, zirconia, calcium hydroxy phosphate, feldspar porcelain powder, barium glass powder, quartz glass powder or sodium aluminum silicate; further preferably a combination of alumina and sodium aluminum silicate;
preferably, the fibers comprise any one or a combination of at least two of glass fibers, quartz fibers, or mullite fibers; further preferably a combination of quartz fibers and mullite fibers;
preferably, the mass ratio of the inorganic powder particles to the fibers is (1-5): 1.
4. A dental machinable composite material according to any of claims 1-3, characterized in that the additives comprise a binder and a dispersant;
preferably, the binder comprises any one of or a combination of at least two of sodium carboxymethylcellulose, polyvinyl alcohol or chitosan;
preferably, the dispersant comprises any one or a combination of at least two of citric acid, acetic acid or Dolapix CE 64;
preferably, the mass of the binder is 1-5% of the mass of the porous preform;
preferably, the mass of the dispersant is 1 to 10% of the mass of the porous preform.
5. A method of producing a dental machinable composite material according to any of claims 1-4, characterized in that the method of producing comprises:
(1) Dispersing fibers, inorganic powder particles and additives in a solvent to obtain slurry;
(2) After directionally freezing the slurry, carrying out freeze drying and sintering treatment to obtain a porous preform;
(3) Silanizing the porous prefabricated body and drying;
(4) And impregnating the porous prefabricated body after the silanization treatment by using a resin impregnating solution, and thermally curing to obtain the dental machinable composite material.
6. The method of preparing a dental machinable composite material according to claim 5, wherein the solvent is water and/or t-butanol;
preferably, the mass ratio of the total mass of the fibers and the inorganic powder particles to the solvent is (1-15): 20.
7. The method for preparing a dental machinable composite material according to claim 5 or 6, wherein the directional freezing is performed at a temperature of-180 to-50 ℃ for 5 to 10min;
preferably, the temperature of the freeze drying is-60 to-40 ℃, and the time is 12 to 24 hours;
preferably, the sintering treatment temperature is 500-800 ℃, and the time is 10min-2h.
8. The method for producing a dental machinable composite material according to any one of claims 5 to 7, wherein the silanization treatment means impregnation of the porous preform with a silane coupling agent;
preferably, the silane coupling agent comprises any one of gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-aminopropyltrimethoxysilane or a combination of at least two thereof;
preferably, the temperature of the silanization treatment is 10-35 ℃, and the time is 3-6h;
preferably, the drying temperature is 60-80 ℃ and the drying time is 10-20h.
9. The method of producing a dental machinable composite material according to any one of claims 5 to 8, wherein the resin impregnating liquid includes a resin and a curing agent;
preferably, the curing agent comprises any one or a combination of at least two of benzoyl peroxide, azobisisobutyronitrile, tert-butyl peroxyacetate or 2-ethyl-4-methylimidazole;
preferably, the mass of the curing agent is 0.1-2% of the total mass of the resin;
preferably, the impregnation temperature is 55-65 ℃ and the impregnation time is 1-2h;
preferably, the temperature of the thermal curing is 80-120 ℃ and the time is 6-20h.
10. Use of a dental machinable composite according to any of claims 1-4 in the manufacture of a dental restorative material.
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Citations (3)
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|---|---|---|---|---|
| US4828493A (en) * | 1986-11-13 | 1989-05-09 | Nippon Oil Co., Ltd. | Denture base |
| CN108743405A (en) * | 2018-06-14 | 2018-11-06 | 中国科学院金属研究所 | A kind of artificial tooth zirconium oxide/resin bionic composite material and preparation method thereof |
| CN112402265A (en) * | 2020-10-13 | 2021-02-26 | 点铂医疗科技（常州）有限公司 | Machinable dental repair material and preparation method thereof |
-
2022
- 2022-12-09 CN CN202211589594.5A patent/CN115944540A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4828493A (en) * | 1986-11-13 | 1989-05-09 | Nippon Oil Co., Ltd. | Denture base |
| CN108743405A (en) * | 2018-06-14 | 2018-11-06 | 中国科学院金属研究所 | A kind of artificial tooth zirconium oxide/resin bionic composite material and preparation method thereof |
| CN112402265A (en) * | 2020-10-13 | 2021-02-26 | 点铂医疗科技（常州）有限公司 | Machinable dental repair material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| MORENA PETRINI: "Fabrication and characterization of biomimetic ceramic/polymer composite materials for dental restoration", DENTAL MATERIALS, vol. 29, 31 December 2013 (2013-12-31), pages 375 - 381 * |
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