CN113800897A - Tricalcium phosphate biological ceramic for photocuring 3d printing, slurry thereof and preparation method thereof - Google Patents
Tricalcium phosphate biological ceramic for photocuring 3d printing, slurry thereof and preparation method thereof Download PDFInfo
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- CN113800897A CN113800897A CN202110942011.1A CN202110942011A CN113800897A CN 113800897 A CN113800897 A CN 113800897A CN 202110942011 A CN202110942011 A CN 202110942011A CN 113800897 A CN113800897 A CN 113800897A
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- tricalcium phosphate
- biological ceramic
- ceramic powder
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- silane coupling
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 101
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 98
- 229940078499 tricalcium phosphate Drugs 0.000 title claims abstract description 98
- 229910000391 tricalcium phosphate Inorganic materials 0.000 title claims abstract description 98
- 235000019731 tricalcium phosphate Nutrition 0.000 title claims abstract description 98
- 239000000919 ceramic Substances 0.000 title claims abstract description 89
- 239000002002 slurry Substances 0.000 title claims abstract description 41
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 21
- 238000007639 printing Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 61
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 239000003462 bioceramic Substances 0.000 claims description 11
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 10
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 7
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 238000000280 densification Methods 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 description 11
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 238000005086 pumping Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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Abstract
The invention discloses a tricalcium phosphate biological ceramic for photocuring 3d printing, slurry and a preparation method thereof, belonging to the technical field of biological ceramic preparation, wherein tricalcium phosphate ceramic powder is dispersed in a solvent to obtain a suspension; adding a silane coupling agent containing alkyl groups and ammonia water into the suspension for pretreatment, and coating a layer of SiO2 film containing alkyl groups with oxide characteristics on the surface of the tricalcium phosphate biological ceramic powder to obtain pretreated tricalcium phosphate biological ceramic powder; and mixing the pretreated tricalcium phosphate biological ceramic powder, a resin monomer, a dispersant and a photoinitiator to obtain tricalcium phosphate biological ceramic slurry. The invention can obviously improve the solid content of the tricalcium phosphate biological ceramic slurry, reduce the sintering shrinkage rate, improve the precision of the sample, promote the sintering densification of the sample and improve the dimensional precision.
Description
Technical Field
The invention belongs to the technical field of biological ceramic preparation, and particularly relates to a tricalcium phosphate biological ceramic for photocuring 3d printing, slurry and a preparation method thereof.
Background
Tricalcium phosphate (beta-TCP) is the main inorganic component of natural bone, has good biocompatibility and degradability, and is a bone scaffold ceramic material which is applied more at present. In order to promote the human osteoblast adhesion, proliferation and differentiation, artificial bone materials generally need to be processed into porous bone scaffolds to be implanted into the human body, but the traditional forming mode of porous ceramics has more limitations: the bone scaffold with complex structure and the pore structure (aperture, shape and distribution) cannot be formed accurately, so that higher requirements are put on the forming process of the artificial bone implant ceramic. The 3d printing technology is utilized to complete the molding of the medical bone scaffold bioceramic, so that the body of a patient can be quickly and conveniently tailored, personalized customization is realized, and the defects are overcome.
The 3d printing method for preparing the tricalcium phosphate bone scaffold biological ceramic mainly comprises a fused deposition molding technology, an ink-jet printing molding technology, a three-dimensional printing molding technology and a photocuring molding technology. Compared with other forming methods, photocuring has the advantages of high precision, printing complex structures and the like, and is the best method for preparing the tricalcium phosphate biological ceramic by 3d printing at present.
Currently, when a photocuring molding technology is adopted to prepare tricalcium phosphate bioceramics (such as CN111825443A and CN109180175A), the following problems exist: (1) the affinity of tricalcium phosphate ceramic powder and resin is poor, so that the solid content of ceramic slurry is low (about 60 wt%), and the mechanical property of a final product is influenced; (2) the resin proportion is not optimized, so that the forming process needs higher exposure power and exposure time, the hole diameter smaller than 0.3mm cannot be printed, and the dimensional precision is influenced; these two major problems have limited the development of stereolithography and tricalcium phosphate bioceramic applications. Although there are patents which try to solve the above problems by adding high refractive index photo-curing resin monomer and ultraviolet absorbent to adjust or using silane coupling agent as dispersant or modified tricalcium phosphate powder, there is no mention of the mechanical properties of bone scaffold and printable pore size (such as CN110330328A, CN109650909A, CN109734434A), or the prepared slurry has low solid content or low mechanical properties of materials (CN107721408A, CN 112274701A).
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a tricalcium phosphate biological ceramic for photocuring 3d printing, slurry and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
according to a first aspect, there is provided a method of preparing a tricalcium phosphate bioceramic slurry for photocuring 3d printing, the method comprising the steps of:
dispersing tricalcium phosphate ceramic powder in a solvent to obtain a suspension;
adding silane coupling agent containing alkyl group and ammonia water into the suspension for pretreatment, and coating a layer of SiO with oxide characteristic and containing alkyl group on the surface of the tricalcium phosphate biological ceramic powder2Filming to obtain pretreated tricalcium phosphate biological ceramic powder;
and mixing the pretreated tricalcium phosphate biological ceramic powder, a resin monomer, a dispersant and a photoinitiator to obtain tricalcium phosphate biological ceramic slurry.
Further, the silane coupling agent containing an alkyl group is preferably a silane coupling agent containing an ethyl group.
Further, the silane coupling agent containing an ethyl group is preferably one or two of ethyltrimethoxysilane, diethyldimethoxysilane and triethylmethoxysilane.
Further, the solvent includes ethanol, acetone, or methanol.
Further, the mass concentration of the ammonia water is 20-25%.
Furthermore, the mass ratio of the tricalcium phosphate ceramic powder, the solvent, the silane coupling agent containing alkyl groups and the ammonia water is preferably (100-200): 200-300): 3.2-4): 20-30.
Further, the pretreatment method comprises the following steps: and condensing and refluxing the suspension added with the silane coupling agent containing alkyl groups for a certain time, and performing suction filtration, washing and drying treatment.
Furthermore, the condensation reflux temperature is 50-70 ℃, and the condensation reflux time is 1-4 h.
Further, the mixing treatment method comprises the following steps: mixing, ball milling and vacuumizing.
Furthermore, the rotating speed of the ball mill is 200-250 r/min, the ball milling time is 4-6 h, and the vacuum pumping is carried out for 0.5 h.
Further, the resin monomer is one or more of isobornyl methacrylate, hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate; the dispersing agent is one or more of KOS-110, BYK-9076 and BYK-163; the initiator is one or more of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, benzoin dimethyl ether and isopropyl thioxanthone.
Furthermore, the mass ratio of the pretreated tricalcium phosphate biological ceramic powder to the resin monomer to the dispersant to the photoinitiator is (190-320): 80: (6-16): 0.8-1.6).
According to a second aspect, a tricalcium phosphate bioceramic slurry for photocuring 3d printing is provided, and is prepared by the method.
According to a third aspect, a tricalcium phosphate biological ceramic for photocuring 3d printing is provided, which is prepared by using the ceramic slurry prepared by the method as a raw material and adopting a photocuring molding technology.
The technical scheme of the invention provides a tricalcium phosphate organism for photocuring 3d printingThe preparation method of the ceramic slurry comprises the steps of pretreating tricalcium phosphate ceramic powder, modifying the tricalcium phosphate ceramic powder by using silane coupling agent containing alkyl groups to coat a layer of SiO with oxide characteristics and containing the alkyl groups on the surface of the tricalcium phosphate ceramic powder2Compared with the existing method, the affinity of the alkyl group contained in the silane coupling agent with a resin monomer can be increased, the solid content of tricalcium phosphate biological ceramic slurry is obviously improved, the sintering shrinkage rate is reduced, the precision of a sample is improved, and the sintering densification of the sample is promoted; in addition, the silicon dioxide has light absorption, can reduce the scattering phenomenon of tricalcium phosphate biological ceramic slurry in the photocuring forming process and the required exposure time in the forming process, combines with resin monomer optimization (monofunctional group monomer improves the affinity with a substrate, trifunctional group or tetrafunctional group monomer improves the strength of a blank body, bifunctional group monomer adjusts the shrinkage rate of resin), improves the size precision, prints the aperture with the size of 0.3mm, and can be used as a mechanical reinforcing phase in the sintering process to improve the mechanical property of the bone scaffold.
Drawings
Fig. 1 is a flow chart of preparation of a tricalcium phosphate bioceramic slurry for photocuring 3d printing.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention. In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details.
It should be noted that, in order to avoid obscuring the present invention by unnecessary details, only the device structure and/or the processing steps closely related to the scheme according to the present invention are shown, and other details not closely related to the present invention are omitted.
Those skilled in the art will appreciate that specific stereolithography techniques are well known in the art and will not be described in detail herein.
The invention provides a preparation method of tricalcium phosphate biological ceramic slurry for photocuring 3d printing, which has the flow shown in figure 1 and comprises the following steps:
(1) dispersing tricalcium phosphate ceramic powder in a solvent, wherein the solvent can be any one of ethanol, acetone and methanol to obtain a suspension;
(2) adding silane coupling agent containing alkyl group and ammonia water into the suspension, wherein the mass concentration of the ammonia water is 20-25% (any value in the range, such as 20%, 21%, 22%, 23%, 24%, 25%), the mass ratio of the tricalcium phosphate ceramic powder, the solvent, the silane coupling agent containing alkyl group and the ammonia water is preferably (100-200): 200-300): 3.2-4): 20-30% (any value in the range, such as (100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200): 200, 210, 220, 230, 240, 250, 260, 270, 280, 290 or 300): 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 or 4): 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30%), performing pretreatment, adding silane coupling agent containing alkyl group, and performing suction filtration for a certain time, and adding silane coupling agent containing alkyl group, and performing suction filtration, Washing and drying, wherein the condensation reflux temperature is 50-70 ℃ (can be any value in the range, such as 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃ and 70 ℃), the condensation reflux time is 1-4 h (can be any value in the range, such as 1h, 2h, 3h and 4h), and the surface of the tricalcium phosphate biological ceramic powder is coated with a layer of SiO with oxide characteristics and containing alkyl groups2And (5) filming to obtain the pretreated tricalcium phosphate biological ceramic powder. The silane coupling agent containing alkyl groups is preferably a silane coupling agent containing ethyl groups, and the silane coupling agent containing ethyl groups is preferably one or two of ethyltrimethoxysilane, diethyldimethoxysilane and triethylmethoxysilane. Under the catalytic action of ammonia water, alkoxy of the silane coupling agent can perform substitution reaction with hydroxyl on the surface of tricalcium phosphate (beta-TCP) powder, so that the hydrophilic and oleophobic properties of the surface of the tricalcium phosphate are changed, the dispersion degree of the tricalcium phosphate powder in the light-cured resin is improved, and the dispersion degree of the tricalcium phosphate powder in the light-cured resin is increasedAnd (3) solid content.
(3) Mixing the pretreated tricalcium phosphate biological ceramic powder, the resin monomer, the dispersing agent and the photoinitiator according to a mass ratio (190-320) of 80 (6-16) to (0.8-1.6) (any ratio within the range can be used, such as (190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310 or 320) to (6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16) to (0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 or 1.6)); then ball milling is carried out, the rotating speed of the ball mill is 200-250 r/min (any value in the range, such as 200r/min, 210r/min, 220r/min, 230r/min, 240r/min and 250r/min), the ball milling time is 4-6 h (any value in the range, such as 4h, 4.5h, 5h, 5.5h and 6 h); vacuumizing for 0.5 h; thus obtaining the tricalcium phosphate biological ceramic slurry. The resin monomer can adopt one or more of isobornyl methacrylate, hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate; the dispersing agent can adopt one or more of KOS-110, BYK-9076 and BYK-163; the initiator can adopt one or more of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, benzoin dimethyl ether and isopropyl thioxanthone.
In order to further understand the present invention, a specific embodiment of a tricalcium phosphate bioceramic slurry for photocuring 3d printing is described in detail below.
Example 1
Step 1: pretreating tricalcium phosphate ceramic powder: firstly, drying tricalcium phosphate ceramic powder for 24 hours at 80 ℃, ultrasonically dispersing by using ethanol as a solvent, transferring the dispersed suspension into a three-neck flask, fully stirring, sequentially adding ethyltrimethoxysilane and ammonia water with the concentration of 20%, performing condensation reflux in a water bath kettle at 50 ℃ for 4 hours, performing suction filtration, washing a sample with ethanol for 4 times, and naturally drying to obtain pretreated tricalcium phosphate biological ceramic powder, wherein the mass ratio of the tricalcium phosphate ceramic powder to the ethanol to the ethyltrimethoxysilane to the ammonia water is 100:200:3.2: 20;
step 2: preparing slurry: and (2) mixing the tricalcium phosphate biological ceramic powder pretreated in the step (1), resin monomers (a mixture of isobornyl methacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate), BYK-163 and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide according to a mass ratio of 200:80:10: 0.8. Mixing, ball milling and vacuum pumping for 0.5h to obtain the tricalcium phosphate biological ceramic slurry. Wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 4 h.
Comparative example 1
Step 1: and preparing slurry, namely preparing untreated tricalcium phosphate ceramic powder, resin monomers (a mixture of isobornyl methacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate), BYK-163 and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide according to the mass ratio of 120:80:6: 0.8. Mixing, ball milling and vacuum pumping for 0.5h to obtain the tricalcium phosphate biological ceramic slurry. Wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 4 h.
Comparative example 2
Step 1: pretreating tricalcium phosphate ceramic powder: firstly, drying tricalcium phosphate ceramic powder for 24 hours at 80 ℃, ultrasonically dispersing by using ethanol as a solvent, transferring the dispersed suspension into a three-neck flask, fully stirring, sequentially adding ethyltrimethoxysilane and ammonia water with the concentration of 20%, performing condensation reflux in a water bath kettle at 50 ℃ for 4 hours, performing suction filtration, washing a sample with ethanol for 4 times, and naturally drying to obtain pretreated tricalcium phosphate biological ceramic powder, wherein the mass ratio of the tricalcium phosphate ceramic powder to the ethanol to the ethyltrimethoxysilane to the ammonia water is 100:200:3.2: 20;
step 2: and (2) preparing slurry, namely preparing tricalcium phosphate biological ceramic powder pretreated in the step (1), resin monomers (a mixture of isobornyl methacrylate and trimethylolpropane triacrylate), BYK-163 and (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide according to the mass ratio of 150:80:7.5: 0.8. Mixing, ball milling and vacuum pumping for 0.5h to obtain the tricalcium phosphate biological ceramic slurry. Wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 4 h.
Example 2
Step 1: pretreating tricalcium phosphate ceramic powder: firstly, drying tricalcium phosphate ceramic powder for 24 hours at 80 ℃, ultrasonically dispersing by using ethanol as a solvent, transferring the dispersed suspension into a three-neck flask, fully stirring, sequentially adding ethyltrimethoxysilane and ammonia water with the concentration of 22%, performing condensation reflux in a water bath kettle at 60 ℃ for 3 hours, performing suction filtration, washing a sample with ethanol for 4 times, and naturally drying to obtain pretreated tricalcium phosphate biological ceramic powder, wherein the mass ratio of the tricalcium phosphate ceramic powder to the ethanol to the ethyltrimethoxysilane to the ammonia water is 150:250:3.5: 25;
step 2: preparing slurry: and (2) mixing the tricalcium phosphate biological ceramic powder pretreated in the step (1), resin monomers (a mixture of hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate), KOS-110 and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide according to a mass ratio of 320:80:16: 1.2. Mixing, ball milling and vacuum pumping for 0.5h to obtain the tricalcium phosphate biological ceramic slurry. Wherein the rotating speed of the ball mill is 250r/min, and the ball milling time is 5 h.
Example 3
Step 1: pretreating tricalcium phosphate ceramic powder: firstly, drying tricalcium phosphate ceramic powder for 24 hours at 80 ℃, ultrasonically dispersing by using ethanol as a solvent, transferring the dispersed suspension into a three-neck flask, fully stirring, sequentially adding ethyltrimethoxysilane and ammonia water with the concentration of 23%, performing condensation reflux in a 70 ℃ water bath kettle for 1 hour, performing suction filtration, washing a sample with ethanol for 4 times, and naturally drying to obtain pretreated tricalcium phosphate biological ceramic powder, wherein the mass ratio of the tricalcium phosphate ceramic powder to the ethanol to the ethyltrimethoxysilane to the ammonia water is 200:300:4: 30;
step 2: preparing slurry: and (2) mixing the tricalcium phosphate ceramic powder pretreated in the step (1), resin monomers (a mixture of isobornyl methacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate), BYK-9076 and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide in a mass ratio of 300:80:15: 0.8. Mixing, ball milling and vacuum pumping for 0.5h to obtain the tricalcium phosphate biological ceramic slurry. Wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 6 h.
Example 4
Step 1: pretreating tricalcium phosphate ceramic powder: firstly, drying tricalcium phosphate ceramic powder for 24 hours at 80 ℃, ultrasonically dispersing by using ethanol as a solvent, transferring the dispersed suspension into a three-neck flask, fully stirring, sequentially adding ethyltrimethoxysilane and ammonia water with the concentration of 24%, performing condensation reflux in a water bath kettle at 50 ℃ for 4 hours, performing suction filtration, washing a sample with ethanol for 4 times, and naturally drying to obtain pretreated tricalcium phosphate biological ceramic powder, wherein the mass ratio of the tricalcium phosphate ceramic powder to the ethanol to the ethyltrimethoxysilane to the ammonia water is 100:200:3.6: 20;
step 2: preparing slurry: and (2) mixing the tricalcium phosphate biological ceramic powder pretreated in the step (1), resin monomers (a mixture of hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate), BYK-163 and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide according to a mass ratio of 190:80:6: 1.6. Mixing, ball milling and vacuum pumping for 0.5h to obtain the tricalcium phosphate biological ceramic slurry. Wherein the rotating speed of the ball mill is 220r/min, and the ball milling time is 4 h.
Example 5
Step 1: pretreating tricalcium phosphate ceramic powder: firstly, drying tricalcium phosphate ceramic powder for 24 hours at 80 ℃, ultrasonically dispersing by using ethanol as a solvent, transferring the dispersed suspension into a three-neck flask, fully stirring, sequentially adding ethyltrimethoxysilane and ammonia water with the concentration of 25%, performing condensation reflux in a water bath kettle at 50 ℃ for 4 hours, performing suction filtration, washing a sample with ethanol for 4 times, and naturally drying to obtain pretreated tricalcium phosphate biological ceramic powder, wherein the mass ratio of the tricalcium phosphate ceramic powder to the ethanol to the ethyltrimethoxysilane to the ammonia water is 100:200:3.2: 20;
step 2: preparing slurry: and (2) mixing the tricalcium phosphate biological ceramic powder pretreated in the step (1), resin monomers (a mixture of hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate), KOS-110 and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide according to a mass ratio of 310:80:12: 1.2. Mixing, ball milling and vacuum pumping for 0.5h to obtain the tricalcium phosphate biological ceramic slurry. Wherein the rotating speed of the ball mill is 250r/min, and the ball milling time is 5 h.
The properties of the products obtained in the examples and comparative examples are shown in Table 1.
TABLE 1 results of performance test of products obtained in examples and comparative examples
As can be seen from table 1, the slurry prepared by pretreating the tricalcium phosphate biological powder according to the embodiment of the present invention has more excellent properties, that is, the solid content, accuracy and mechanical properties of examples 1 to 5 are better than those of comparative examples 1 and 2, because: the alkyl group contained in the silane coupling agent can increase the affinity with the resin monomer, remarkably improve the solid content of the tricalcium phosphate biological ceramic slurry, reduce the sintering shrinkage rate, improve the precision of the sample and promote the sintering densification of the sample; in addition, the silicon dioxide has light absorption, can reduce scattering phenomenon of tricalcium phosphate biological ceramic slurry in the photocuring forming process and exposure time required in the forming process, and is combined with resin monomer optimization, namely, a monofunctional monomer improves affinity with a substrate, a trifunctional or tetrafunctional monomer improves strength of a blank body, a bifunctional monomer adjusts shrinkage of resin (a bifunctional monomer is not added to adjust the shrinkage of resin in a comparative example 2), size precision is improved, the printing size is 0.3mm of aperture, and the silicon dioxide can be used as a mechanical reinforcing phase in the sintering process, so that mechanical properties of a bone scaffold are improved.
Features that are described and/or illustrated above with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein, is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
The many features and advantages of these embodiments are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of these embodiments which fall within the true spirit and scope thereof. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the embodiments of the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope thereof.
The invention has not been described in detail and is in part known to those of skill in the art.
Claims (10)
1. A preparation method of tricalcium phosphate biological ceramic slurry for photocuring 3d printing is characterized by comprising the following steps:
dispersing tricalcium phosphate ceramic powder in a solvent to obtain a suspension;
adding silane coupling agent containing alkyl group and ammonia water into the suspension for pretreatment, and coating a layer of SiO with oxide characteristic and containing alkyl group on the surface of the tricalcium phosphate biological ceramic powder2Filming to obtain pretreated tricalcium phosphate biological ceramic powder;
and mixing the pretreated tricalcium phosphate biological ceramic powder, a resin monomer, a dispersant and a photoinitiator to obtain tricalcium phosphate biological ceramic slurry.
2. The method of claim 1, wherein the solvent is ethanol, acetone, or methanol.
3. The method according to claim 1, wherein the silane coupling agent containing alkyl groups is selected from silane coupling agents containing ethyl groups, and the silane coupling agent containing ethyl groups is one or two of ethyltrimethoxysilane, diethyldimethoxysilane and triethylmethoxysilane.
4. The method of claim 1, wherein the mass concentration of the ammonia water is 20-25%, and the mass ratio of the tricalcium phosphate ceramic powder, the solvent, the silane coupling agent containing alkyl groups and the ammonia water is (100-200): (200-300): (3.2-4): (20-30).
5. The method of claim 1, wherein the pre-processing is performed by: and condensing and refluxing the suspension added with the silane coupling agent containing the alkyl group for a certain time, and performing suction filtration, washing and drying treatment, wherein the condensing and refluxing temperature is 50-70 ℃, and the condensing and refluxing time is 1-4 h.
6. The method of claim 1, wherein the mixing process is performed by: firstly, mixing; then ball milling is carried out, the rotating speed of the ball mill is 200-250 r/min, and the ball milling time is 4-6 h; finally vacuumizing for 0.5 h.
7. The method of claim 1, wherein the resin monomer is one or more of isobornyl methacrylate, hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate; the dispersing agent is one or more of KOS-110, BYK-9076 and BYK-163; the initiator is one or more of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, benzoin dimethyl ether and isopropyl thioxanthone.
8. The method of claim 1 or 7, wherein the mass ratio of the pretreated tricalcium phosphate bioceramic powder to the resin monomer to the dispersant to the photoinitiator is (190-320): 80 (6-16): 0.8-1.6).
9. A photocurable tricalcium phosphate bioceramic slurry for 3d printing, prepared by the process of any one of claims 1 to 8.
10. A photocured 3d printing tricalcium phosphate bioceramic prepared by using a photocuring molding technique, wherein the tricalcium phosphate bioceramic is prepared from the ceramic slurry prepared by the method of any one of claims 1 to 8.
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