CN116063037B - Preparation method of Eu modified calcium silicate carbide bone cement - Google Patents
Preparation method of Eu modified calcium silicate carbide bone cement Download PDFInfo
- Publication number
- CN116063037B CN116063037B CN202111290812.0A CN202111290812A CN116063037B CN 116063037 B CN116063037 B CN 116063037B CN 202111290812 A CN202111290812 A CN 202111290812A CN 116063037 B CN116063037 B CN 116063037B
- Authority
- CN
- China
- Prior art keywords
- bone cement
- carbide
- tricalcium
- modified
- tricalcium silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002639 bone cement Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 7
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims abstract description 43
- 235000019976 tricalcium silicate Nutrition 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 32
- 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 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000009423 ventilation Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 229910052918 calcium silicate Inorganic materials 0.000 abstract description 4
- 239000000378 calcium silicate Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 7
- 210000000988 bone and bone Anatomy 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010061728 Bone lesion Diseases 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000028709 inflammatory response Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/02—Portland cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00137—Injection moldable mixtures
Abstract
The invention belongs to the field of material science and engineering, and particularly relates to a preparation method of Eu modified carbonized tricalcium silicate bone cement. A preparation method of Eu modified carbonized tricalcium silicate bone cement comprises the following steps: s1, preparing tricalcium silicate powder by a sol-gel method; s2, carbonizing the tricalcium silicate powder to obtain carbonized tricalcium silicate; s3, preparing Eu-doped hydroxyapatite powder; and S4, uniformly mixing the Eu-doped hydroxyapatite powder prepared in the step S3 with the tricalcium carbide prepared in the step S2 to obtain the Eu-modified tricalcium carbide bone cement. The invention discloses a preparation method of Eu modified tricalcium silicate carbide bone cement, which has the following beneficial effects: 1. the mechanical strength is greatly improved; 2. the injectability of the calcium silicate carbide bone cement is improved; 3. the setting time of the carbonized tricalcium silicate bone cement is reduced; 4. reduces the alkalinity of the carbonized tricalcium silicate bone cement.
Description
Technical Field
The invention belongs to the field of material science and engineering, and particularly relates to a preparation method of Eu modified carbonized tricalcium silicate bone cement.
Background
The hard tissues of the human body are mainly composed of the biomineral hydroxyapatite (HAp) and protein collagen, and do not have a complete self-repairing ability, which often severely affects the normal life of people.
At present, in the field of bone filling, excellent autologous bone grafting sources are limited, and other traditional bone repair materials have no good biocompatibility, degradability and the like. However, the present-day synthetic bone cements can avoid these disadvantages to some extent, and in particular, calcium silicate-based bone cements have received a great deal of attention because of their good bioactivity, degradability, and excellent osteogenic properties.
Tricalcium silicate (C 3 S) has been widely used as a filler for bone defects, as a representative of portland cement, having bioactivity, biodegradability and antibacterial properties. In vitro experimental studies, C 3 S had a suitable degradation rate and induced bone-like apatite formation. The calcium silicate can degrade in vivo to release silicon element and promote bone growth of human body. And plays an important role in the orthopaedics field due to its self-consolidation characteristics, bioactivity and ability to fill irregular shape defects. Although C 3 S bone cement has many advantages, it produces calcium hydroxide (Ca (OH) 2) upon hydration, which results in early stages of implantation in high alkalinity and inflammatory response. Although the pH of carbonated tricalcium silicate (V-C 3 S) during hydration can be successfully reduced by the reaction with Ca (OH) 2 by the input of carbon dioxide (CO 2), it has better biocompatibility. But the carbonated bone cement has reduced mechanical strength compared to pure C 3 S. How to provide the mechanical strength of carbonated tricalcium silicate is an urgent problem to be solved.
Disclosure of Invention
The invention aims to: the invention improves the problems existing in the prior art, namely, the invention discloses a preparation method of Eu modified tricalcium carbide bone cement.
The technical scheme is as follows: a preparation method of Eu modified carbonized tricalcium silicate bone cement comprises the following steps:
S1, preparing tricalcium silicate powder by a sol-gel method;
s2, carbonizing the tricalcium silicate powder to obtain carbonized tricalcium silicate;
S3, preparing Eu-doped hydroxyapatite powder;
And S4, uniformly mixing the Eu-doped hydroxyapatite powder prepared in the step S3 with the tricalcium carbide prepared in the step S2 to obtain the Eu-modified tricalcium carbide bone cement.
Further, the Eu doping concentration in the Eu-modified tricalcium carbide bone cement is 0.5-2%, preferably 1%.
Further, step S1 includes the steps of, in terms of parts by mole:
S11, respectively adding 8-12 parts of nitric acid aqueous solution and 8-12 parts of absolute ethyl alcohol into 1 part of tetraethyl orthosilicate to obtain mixed solution;
S12, adding 1 part of Ca (NO 3)2·4H2 O into the mixed solution, and continuously stirring for 0.5-2 h to obtain a sol solution;
S13, sealing the sol solution, aging for 36-72 hours at 55-65 ℃, and then drying in a baking oven at 110-130 ℃ to obtain gel;
S14, placing the gel into a muffle furnace, heating to 1430-1470 ℃ at a speed of 4-6 ℃/min, preserving heat for 6-12 h, and cooling along with the furnace to obtain a sintered body;
S15, crushing and sieving the sintered blocks, and drying in an oven at 55-65 ℃ to obtain the tricalcium silicate powder.
Further, the concentration of the aqueous nitric acid solution in step S11 is 1 to 3M.
Further, the screen in step S15 is a 250 mesh screen.
Further, step S2 includes the steps of:
s21, according to the liquid-powder ratio of 2-4: 1, mixing and uniformly stirring tricalcium silicate powder and deionized water, and placing the mixture into a constant temperature and humidity curing box, wherein the temperature is 37 ℃ and the humidity is 100% for curing for 4-6 hours to obtain a mixed solution;
S22, introducing carbon dioxide into the mixed solution at a rate of 1-2L/min for 20-40 min, continuously maintaining 100% humidity in the ventilation process, and stirring once every 5-10 min to obtain a reaction solution after completion;
s23, taking out the reaction solution, drying for 12-48 hours at 100-120 ℃, grinding and sieving to obtain the tricalcium carbide.
Further, a 250 mesh screen is passed in step S23.
Further, the step S3 includes the following steps in parts by mole:
s31, 20 parts of Ca (NO 3)2·4H2 O, 0.2-0.8 part (Eu (NO 3)3·6H2 O, 24 parts (NH 4)2HPO4 is dissolved in 8333 parts of deionized water) is mixed to obtain a mixed solution;
s32, regulating the pH value of the mixed solution to 10-10.5 by ammonia water, and stirring for 5-20 minutes to obtain a mixture;
s33, injecting the mixture into a hydrothermal reaction kettle, aging for 5-7 hours at 140-160 ℃, and obtaining a reaction product after the reaction is finished;
s34, centrifuging the reaction product to obtain a precipitate, and drying the precipitate at 65-75 ℃ for 10-16 hours to obtain the Eu-doped hydroxyapatite powder.
Further, in step S31 (Eu (NO 3)3·6H2 O is used in an amount of 0.4 parts).
Further, the concentration of ammonia water in step S32 is 20 to 30%.
The beneficial effects are that: the invention discloses a preparation method of Eu modified tricalcium silicate carbide bone cement, which has the following beneficial effects:
1. The mechanical strength is greatly improved, namely the compression resistance is slightly increased from 8.28+/-0.21 MPa to 20.98 +/-0.56 MPa, and the compression resistance is improved by about 153 percent.
2. The injectability of the calcium silicate carbide bone cement is improved;
3. reduces the setting time of the tricalcium silicate carbide bone cement, namely from 13.54 plus or minus 0.37min to 9.92 plus or minus 0.21min;
4. reduces the alkalinity of the carbonized tricalcium silicate bone cement.
Drawings
FIG. 1 is a schematic diagram showing the relationship between Eu doping concentration and injectability in Eu-modified tricalcium silicate carbide bone cement prepared by the present invention.
FIG. 2 is a schematic diagram showing the relationship between Eu doping concentration and setting time in Eu-modified tricalcium silicate carbide bone cement prepared in accordance with the present invention.
FIG. 3 is a schematic diagram showing the relationship between Eu doping concentration and porosity in Eu-modified tricalcium silicate carbide bone cement prepared by the present invention.
FIG. 4 is a graph showing the relationship between Eu doping concentration and compressive strength in Eu-modified tricalcium silicate carbide bone cement prepared in accordance with the present invention.
FIG. 5 is a graph showing the relationship between Eu doping concentration and pH in Eu-modified tricalcium silicate carbide bone cement prepared in accordance with the present invention.
The specific embodiment is as follows:
The following detailed description of specific embodiments of the invention.
Example 1
A preparation method of Eu modified carbonized tricalcium silicate bone cement comprises the following steps:
S1, preparing tricalcium silicate powder by a sol-gel method;
s2, carbonizing the tricalcium silicate powder to obtain carbonized tricalcium silicate;
S3, preparing Eu-doped hydroxyapatite powder;
And S4, uniformly mixing the Eu-doped hydroxyapatite powder prepared in the step S3 with the tricalcium carbide prepared in the step S2 to obtain the Eu-modified tricalcium carbide bone cement.
Further, the Eu doping concentration in the Eu-modified tricalcium carbide bone cement is 1%.
Further, step S1 includes the steps of, in terms of parts by mole:
S11, respectively adding 10 parts of nitric acid aqueous solution and 10 parts of absolute ethyl alcohol into 1 part of tetraethyl orthosilicate to obtain mixed solution;
S12, adding 1 part of Ca (NO 3)2·4H2 O into the mixed solution, and continuously stirring for 1h to obtain a sol solution;
S13, sealing the sol solution, aging for 48 hours at 60 ℃, and drying in an oven at 120 ℃ to obtain gel;
S14, placing the gel into a muffle furnace, heating to 1430-1450 ℃ at a speed of 5 ℃/min, preserving heat for 8 hours, and cooling along with the furnace to obtain a sintered body;
S15, crushing and sieving the sintered blocks, and drying in an oven at 60 ℃ to obtain tricalcium silicate powder.
Further, the concentration of the aqueous nitric acid solution in step S11 is 2M.
Further, the screen in step S15 is a 250 mesh screen.
Further, step S2 includes the steps of:
S21, according to the liquid-powder ratio of 3:1, mixing and uniformly stirring tricalcium silicate powder and deionized water, and placing the mixture into a constant temperature and humidity curing box for curing at 37 ℃ and 100% humidity for 5 hours to obtain a mixed solution;
S22, introducing carbon dioxide into the mixed solution at a speed of 1.5L/min for 30min, continuously maintaining 100% humidity in the ventilation process, and stirring once every 6min to obtain a reaction solution after the completion of the ventilation;
s23, taking out the reaction solution, drying at 110 ℃ for 24 hours, grinding and sieving to obtain the tricalcium carbide.
Further, a 250 mesh screen is passed in step S23.
Further, the step S3 includes the following steps in parts by mole:
S31, a mixed solution was obtained by dissolving 20 parts of Ca (NO 3)2·4H2 O, 0.4 parts (Eu (NO 3)3·6H2 O, 24 parts (NH 4)2HPO4 in 8333 parts of deionized water;
S32, regulating the pH value of the mixed solution to 10.25 by ammonia water, and stirring for 10 minutes to obtain a mixture;
S33, injecting the mixture into a hydrothermal reaction kettle, aging for 6 hours at 150 ℃, and obtaining a reaction product after the reaction is finished;
S34, centrifuging the reaction product to obtain a precipitate, and drying the precipitate at 70 ℃ for 12 hours to obtain the Eu-doped hydroxyapatite powder.
Further, the concentration of ammonia water in step S32 is 25%.
Example 2
A preparation method of Eu modified carbonized tricalcium silicate bone cement comprises the following steps:
S1, preparing tricalcium silicate powder by a sol-gel method;
s2, carbonizing the tricalcium silicate powder to obtain carbonized tricalcium silicate;
S3, preparing Eu-doped hydroxyapatite powder;
And S4, uniformly mixing the Eu-doped hydroxyapatite powder prepared in the step S3 with the tricalcium carbide prepared in the step S2 to obtain the Eu-modified tricalcium carbide bone cement.
Further, the Eu doping concentration in the Eu modified tricalcium silicate carbide bone cement is 0.5%.
Further, step S1 includes the steps of, in terms of parts by mole:
S11, respectively adding 8 parts of nitric acid aqueous solution and 8 parts of absolute ethyl alcohol into 1 part of tetraethyl orthosilicate to obtain mixed solution;
S12, adding 1 part of Ca (NO 3)2·4H2 O into the mixed solution, and continuously stirring for 0.5h to obtain a sol solution;
S13, sealing the sol solution, aging for 72 hours at 55 ℃, and then drying in a baking oven at 110 ℃ to obtain gel;
S14, placing the gel into a muffle furnace, heating to 1430 ℃ at a speed of 4 ℃/min, preserving heat for 12 hours, and cooling along with the furnace to obtain a sintered body;
s15, crushing and sieving the sintered blocks, and drying in an oven at 55 ℃ to obtain tricalcium silicate powder.
Further, the concentration of the aqueous nitric acid solution in step S11 is 1M.
Further, the screen in step S15 is a 250 mesh screen.
Further, step S2 includes the steps of:
S21, according to the liquid-powder ratio of 2:1, mixing and uniformly stirring tricalcium silicate powder and deionized water, and placing the mixture into a constant temperature and humidity curing box for curing for 4 hours at 37 ℃ and 100% humidity to obtain a mixed solution;
s22, introducing carbon dioxide into the mixed solution at a speed of 1L/min for 40min, continuously maintaining 100% humidity in the ventilation process, and stirring for once every 5min to obtain a reaction solution after completion;
s23, taking out the reaction solution, drying at 100 ℃ for 48 hours, grinding and sieving to obtain the tricalcium carbide.
Further, a 250 mesh screen is passed in step S23.
Further, the step S3 includes the following steps in parts by mole:
S31, a mixed solution was obtained by dissolving 20 parts of Ca (NO 3)2·4H2 O, 0.2 parts (Eu (NO 3)3·6H2 O, 24 parts (NH 4)2HPO4 in 8333 parts of deionized water;
S32, regulating the pH value of the mixed solution to 10 by ammonia water, and stirring for 5 minutes to obtain a mixture;
s33, injecting the mixture into a hydrothermal reaction kettle, aging for 7 hours at 140 ℃, and obtaining a reaction product after the reaction is finished;
S34, centrifuging the reaction product to obtain a precipitate, and drying the precipitate at 65 ℃ for 16 hours to obtain the Eu-doped hydroxyapatite powder.
Further, the concentration of ammonia water in step S32 is 20%.
Example 3
A preparation method of Eu modified carbonized tricalcium silicate bone cement comprises the following steps:
S1, preparing tricalcium silicate powder by a sol-gel method;
s2, carbonizing the tricalcium silicate powder to obtain carbonized tricalcium silicate;
S3, preparing Eu-doped hydroxyapatite powder;
And S4, uniformly mixing the Eu-doped hydroxyapatite powder prepared in the step S3 with the tricalcium carbide prepared in the step S2 to obtain the Eu-modified tricalcium carbide bone cement.
Further, the Eu doping concentration in the Eu-modified tricalcium carbide bone cement is 2%.
Further, step S1 includes the steps of, in terms of parts by mole:
S11, respectively adding 12 parts of nitric acid aqueous solution and 12 parts of absolute ethyl alcohol into 1 part of tetraethyl orthosilicate to obtain mixed solution;
S12, adding 1 part of Ca (NO 3)2·4H2 O into the mixed solution, and continuously stirring for 2 hours to obtain a sol solution;
S13, sealing the sol solution, aging for 36 hours at 65 ℃, and then drying in a drying oven at 130 ℃ to obtain gel;
S14, placing the gel into a muffle furnace, heating to 1470 ℃ at a speed of 6 ℃/min, preserving heat for 6 hours, and cooling along with the furnace to obtain a sintered body;
s15, crushing and sieving the sintered blocks, and drying in an oven at 65 ℃ to obtain tricalcium silicate powder.
Further, the concentration of the aqueous nitric acid solution in step S11 is 3M.
Further, the screen in step S15 is a 250 mesh screen.
Further, step S2 includes the steps of:
S21, according to the liquid-powder ratio of 4:1, mixing and uniformly stirring tricalcium silicate powder and deionized water, and placing the mixture into a constant temperature and humidity curing box for curing at 37 ℃ and 100% humidity for 6 hours to obtain a mixed solution;
S22, introducing carbon dioxide into the mixed solution at a rate of 2L/min for 20min, continuously maintaining 100% humidity in the ventilation process, and stirring for once every 10min to obtain a reaction solution after completion;
S23, taking out the reaction solution, drying at 120 ℃ for 12 hours, grinding and sieving to obtain the tricalcium carbide.
Further, a 250 mesh screen is passed in step S23.
Further, the step S3 includes the following steps in parts by mole:
S31, a mixed solution was obtained by dissolving 20 parts of Ca (NO 3)2·4H2 O, 0.8 part (Eu (NO 3)3·6H2 O, 24 parts (NH 4)2HPO4 in 8333 parts of deionized water;
S32, regulating the pH value of the mixed solution to 10.5 by ammonia water, and stirring for 20 minutes to obtain a mixture;
S33, injecting the mixture into a hydrothermal reaction kettle, aging for 5 hours at 160 ℃, and obtaining a reaction product after the reaction is finished;
s34, centrifuging the reaction product to obtain a precipitate, and drying the precipitate at 75 ℃ for 10 hours to obtain the Eu-doped hydroxyapatite powder.
Further, the concentration of ammonia water in step S32 is 30%.
Verification test:
Eu modified tricalcium silicate carbide bone cement was prepared according to the process parameters of specific example 1, except that:
Mixing Eu-doped hydroxyapatite powder prepared in the step S3 and tricalcium carbide prepared in the step S2 in different proportions, preparing mixed powder with Eu doping concentration of 0, 0.5%, 1%, 1.5% and 2wt%, fully grinding the mixed powder by using a mortar to completely mix the two powder, and mixing and solidifying the mixed powder with dipotassium hydrogen phosphate solution respectively, wherein the liquid-powder ratio is 0.3ml/g. After stirring into paste, the solution is immediately injected into a mold (phi 6mm x 3mm or phi 6mm x 12 mm) to obtain a uniform shape, and after demolding, curing is performed for 3 days in a drying oven (37 ℃ and 100% humidity), and then the temperature is raised to 60 ℃ and drying is performed, so that the Eu: HAp/V-C3S composite material is obtained. The Eu: HAp/V-C3S composite materials were named Eu-0, eu-0.5, eu-1, eu-1.5 and Eu-2, respectively, in terms of Eu doping concentrations of 0%, 0.5%, 1.5% and 2% by weight.
1. Injection rate
The injectability of the bone cement samples was tested using a medical syringe (5 ml volume, 2mm injection caliber). Mixing the Eu: V-C 3 S powder and the curing solution, wherein the weight is denoted as M1, and then injecting the mixed slurry into a syringe. The slurry was manually extruded after 60s, at which time the weight of the extrudate was recorded as M2. The injectability values are calculated from formula (1):
FIG. 1 is a schematic diagram showing the relationship between Eu doping concentration and injectability in Eu-modified tricalcium silicate carbide bone cement prepared by the present invention. As can be seen from fig. 1: the addition of Eu greatly ameliorates this problem, and the injectability of bone cement pastes has been increasing from Eu-0 to Eu-2.
2. Coagulation time
The setting time of Eu: HAp/V-C3S bone cement composite was measured with a 400g Gilmore needle having a diameter of 1mm in accordance with ISO 9917-1 standard, and then it was observed that the Gilmore needle did not generate indentation points exceeding a depth of 1mm at different areas of the bone cement cross section in the mold. 6 experiments were performed and the average was taken.
Setting time of bone cement is one of the important indexes for evaluating it. It is desirable to provide sufficient surgical time for the clinical procedure, while also providing efficacy in a short time after the end of the procedure. The setting time of the bone cement should be controlled between 6 and 15 minutes, which corresponds to the optimal time required for the operation. FIG. 2 is a schematic diagram showing the relationship between Eu doping concentration and setting time in Eu-modified tricalcium silicate carbide bone cement prepared in accordance with the present invention. The results show that from Eu-0 to Eu-2, the setting time of the bone cement is shortened from 13.54.+ -. 0.37min to 9.92.+ -. 0.21min.
3 Compressive Strength and porosity
The Eu: HAp/V-C3S bone cement cylindrical sample (phi 6mm x12 mm) prepared by the above-mentioned demolding was subjected to compressive strength test after polishing. Bone cement samples were compressed using a universal material tester (TFW-2S, shanghai Tuo Feng instruments Co., ltd., china) at a rate of 0.5 mm/min. 6 experiments were performed and the average was taken.
The porosity of Eu: V-C3S composites was measured according to ISO Standard 39231/1-1979 (E) using the liquid displacement (Archimedes) method. First, the bone cement sample was dried in a dry oven, at which time the dry weight was measured and recorded as M3. Then placing the sample in a suction bottle filled with deionized water, vacuumizing for 30 minutes to ensure that air is exhausted, and taking out the sample to remove water drops on the surface. The wet weight of the weighed sample at this time was recorded as M4. Finally, the sample was suspended in deionized water to give a suspended weight designated M5. The density of water is represented by ρ value, and the porosity value is calculated by formula (2):
FIG. 3 is a schematic diagram showing the relationship between Eu doping concentration and porosity in Eu-modified tricalcium silicate carbide bone cement prepared by the present invention. FIG. 4 is a graph showing the relationship between Eu doping concentration and compressive strength in Eu-modified tricalcium silicate carbide bone cement prepared in accordance with the present invention.
For bone surgery, the bone repair material must have a certain mechanical strength. The porosity of the material also has a certain effect on the growth of bone cells at the bone lesion. Therefore, it is necessary to measure the compressive strength and porosity of the Eu: HAp/V-C 3 S cylindrical bone cement sample. Fig. 3 and 4 show that the numerical changes in compressive strength and porosity of the samples show opposite trends as the Eu content increases. With the increase of Eu content, the compressive strength follows the rule of increasing first and then decreasing, from 0 to 0.5wt%, and the strength value is increased from 8.28+/-0.21 MPa to 20.98 +/-0.56 MPa. As the Eu content continues to increase to 1wt%, a small decrease in compressive strength begins to occur. And when the content is increased to 2wt%, the strength value is reduced from about 20Mpa to 6.76Mpa + -0.39 Mpa.
Meanwhile, the porosity change trend of the bone cement sample is opposite to the compressive strength, and the porosity change trend is reduced and then increased. As the europium content increases from 0 to 0.5wt%, the porosity decreases from 45.80% ± 0.52% to 36.78% ± 0.24%. Also, as the europium content increases from 0.5wt% to 2wt%, the porosity increases from 36.78% + -0.24% to 47.46% + -0.15%. The compressive strength of Eu-0.5 is 20.98 +/-0.56 MPa, which is 141.06 percent higher than that of Eu-0. The porosity of Eu-0.5 is 36.78% + -0.24%, which is 19.69% lower than that of Eu-0.
4. PH value of
The prepared bone cement sample was immersed in SBF solution at a liquid-to-powder ratio of 20mL/g, and then the pH value of Eu: V-C3S powder in SBF solution was measured with a pH meter (PHSJ-3F, rex, shanghai, china) at 1,3, 5 and 7 days for 4 time points during the immersion.
The pH is the result of the release of one ion from the bone cement in the simulated fluid. FIG. 5 is a graph showing the relationship between Eu doping concentration and pH in Eu-modified tricalcium silicate carbide bone cement prepared in accordance with the present invention. As can be seen from FIG. 5, the V-C3Ss of the europium-doped composite materials were immersed in the SBF solution for various periods of time at pH values. After the Eu-C3S bone cement is soaked for 1-3 days, the pH value of the SBF is increased along with the increase of soaking time and tends to be slower, and the pH value is rapidly increased and then is reduced after soaking for 3-7 days. Wherein the pH increasing trend of Eu-0.5 and Eu-1 is at a lower level in several groups of samples.
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various modifications may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (7)
1. The preparation method of the Eu modified carbonized tricalcium silicate bone cement is characterized by comprising the following steps of:
S1, preparing tricalcium silicate powder by a sol-gel method;
s2, carbonizing the tricalcium silicate powder to obtain carbonized tricalcium silicate;
S3, preparing Eu-doped hydroxyapatite powder;
S4, uniformly mixing the Eu-doped hydroxyapatite powder prepared in the step S3 with the tricalcium carbide silicate prepared in the step S2 to obtain the Eu-modified tricalcium carbide bone cement, wherein:
the doping concentration of Eu in the Eu modified calcium silicate carbide bone cement is 0.5-2%;
Step S2 comprises the steps of:
s21, according to the liquid-powder ratio of 2-4: 1, mixing and uniformly stirring tricalcium silicate powder and deionized water, and placing the mixture into a constant temperature and humidity curing box, wherein the temperature is 37 ℃ and the humidity is 100% for curing for 4-6 hours to obtain a mixed solution;
S22, introducing carbon dioxide into the mixed solution at a rate of 1-2L/min for 20-40 min, continuously maintaining 100% humidity in the ventilation process, and stirring once every 5-10 min to obtain a reaction solution after completion;
S23, taking out the reaction solution, drying for 12-48 hours at 100-120 ℃, grinding and sieving to obtain tricalcium carbide;
The step S3 comprises the following steps in parts by mole:
s31, 20 parts of Ca (NO 3)2·4H2 O, 0.2-0.8 part (Eu (NO 3)3·6H2 O, 24 parts (NH 4)2HPO4 is dissolved in 8333 parts of deionized water) is mixed to obtain a mixed solution;
s32, regulating the pH value of the mixed solution to 10-10.5 by ammonia water, and stirring for 5-20 minutes to obtain a mixture;
s33, injecting the mixture into a hydrothermal reaction kettle, aging for 5-7 hours at 140-160 ℃, and obtaining a reaction product after the reaction is finished;
s34, centrifuging the reaction product to obtain a precipitate, and drying the precipitate at 65-75 ℃ for 10-16 hours to obtain the Eu-doped hydroxyapatite powder.
2. The method for producing Eu-modified tricalcium silicate carbide bone cement of claim 1, characterized in that the Eu doping concentration in the Eu-modified tricalcium silicate carbide bone cement is 1%.
3. The method for preparing Eu-modified tricalcium carbide bone cement of claim 1, wherein the step S1 comprises the steps of, in terms of parts by mole:
S11, respectively adding 8-12 parts of nitric acid aqueous solution and 8-12 parts of absolute ethyl alcohol into 1 part of tetraethyl orthosilicate to obtain mixed solution;
S12, adding 1 part of Ca (NO 3)2·4H2 O into the mixed solution, and continuously stirring for 0.5-2 h to obtain a sol solution;
S13, sealing the sol solution, aging for 36-72 hours at 55-65 ℃, and then drying in a baking oven at 110-130 ℃ to obtain gel;
S14, placing the gel into a muffle furnace, heating to 1430-1470 ℃ at a speed of 4-6 ℃/min, preserving heat for 6-12 h, and cooling along with the furnace to obtain a sintered body;
S15, crushing and sieving the sintered blocks, and drying in an oven at 55-65 ℃ to obtain the tricalcium silicate powder.
4. The method for producing Eu-modified tricalcium silicate carbide bone cement of claim 3, wherein the concentration of the nitric acid aqueous solution in step S11 is 1 to 3M, and the mesh screen in step S15 is a 250 mesh screen.
5. The method for preparing Eu-modified tricalcium carbide bone cement of claim 1, wherein the step S23 is performed through a 250 mesh screen.
6. The method for producing Eu-modified tricalcium silicate carbide bone cement of claim 1, wherein in step S31 (Eu (NO 3)3·6H2 O is used in an amount of 0.4 parts).
7. The method for preparing Eu-modified tricalcium silicate carbide bone cement of claim 1, characterized in that the concentration of ammonia water in step S32 is 20-30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111290812.0A CN116063037B (en) | 2021-11-02 | 2021-11-02 | Preparation method of Eu modified calcium silicate carbide bone cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111290812.0A CN116063037B (en) | 2021-11-02 | 2021-11-02 | Preparation method of Eu modified calcium silicate carbide bone cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116063037A CN116063037A (en) | 2023-05-05 |
| CN116063037B true CN116063037B (en) | 2024-04-19 |
Family
ID=86168669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111290812.0A Active CN116063037B (en) | 2021-11-02 | 2021-11-02 | Preparation method of Eu modified calcium silicate carbide bone cement |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116063037B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157045A (en) * | 2007-10-26 | 2008-04-09 | 中国科学院上海硅酸盐研究所 | Complex self-curing material, method and application of bioactivity calcium phosphate/tricalcium silicate |
| CN105311680A (en) * | 2015-11-20 | 2016-02-10 | 华南理工大学 | Preparation method of calcium phosphate bone cement simultaneously releasing zinc ions and silicate ions |
| CN108249414A (en) * | 2016-12-28 | 2018-07-06 | 浙江美加华医疗技术有限公司 | A kind of rear-earth-doped hydroxyapatite nanoparticle and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060198863A1 (en) * | 2005-03-03 | 2006-09-07 | Musculoskeletal Transplant Foundation | Ceramic composition for filling bone defects |
-
2021
- 2021-11-02 CN CN202111290812.0A patent/CN116063037B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157045A (en) * | 2007-10-26 | 2008-04-09 | 中国科学院上海硅酸盐研究所 | Complex self-curing material, method and application of bioactivity calcium phosphate/tricalcium silicate |
| CN105311680A (en) * | 2015-11-20 | 2016-02-10 | 华南理工大学 | Preparation method of calcium phosphate bone cement simultaneously releasing zinc ions and silicate ions |
| CN108249414A (en) * | 2016-12-28 | 2018-07-06 | 浙江美加华医疗技术有限公司 | A kind of rear-earth-doped hydroxyapatite nanoparticle and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116063037A (en) | 2023-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101157045B (en) | Complex self-curing material, method and application of bioactivity calcium phosphate/tricalcium silicate | |
| EP1743661B1 (en) | Method of controlling average pore diameter of porous material containing apatite/collagen composite fiber | |
| CN108635624B (en) | Anti-collapsibility injectable magnesium phosphate-based bone cement | |
| US7118705B2 (en) | Method for making a molded calcium phosphate article | |
| CN101053673B (en) | High strength and tenacity degradable strontium calcium superphosphate composite bone cement and its preparation method | |
| JPS6242625B2 (en) | ||
| CN109395160B (en) | Rapidly degradable injectable bone cement and application thereof | |
| CN107032775B (en) | Nano-hydroxyapatite and dicalcium silicate composite bioceramic and preparation method and application thereof | |
| CN111773432A (en) | Magnesium-based amorphous-calcium phosphate/calcium silicate composite filler and preparation and application thereof | |
| CN100406072C (en) | Bio-activity tricalcium silicate/semi water calcium sulphate composite self-solidification material, preparation and application | |
| CN109331223B (en) | Medicine-carrying bioactive glass composite calcium phosphate bone cement and application thereof | |
| TWI529152B (en) | A degradable magnesium-calcium silicate bone cement and producing method thereof | |
| JPS6272363A (en) | Medical or dental cement composition | |
| US6648960B1 (en) | Method of shortening a working and setting time of a calcium phosphate cement (CPC) paste | |
| CN116063037B (en) | Preparation method of Eu modified calcium silicate carbide bone cement | |
| CN103830774B (en) | A kind of bone cement and preparation method thereof | |
| CN108653804B (en) | Preparation method of silicon-doped calcium phosphate bone repair material | |
| Balgová et al. | Synthesis of poly (vinyl alcohol)—hydroxyapatite composites and characterization of their bioactivity | |
| CN110665056B (en) | Injectable bone cement with tissue self-bonding performance and preparation method and application thereof | |
| US20160022864A1 (en) | Tiny Bone Defect Repairing Material, Matrix Material Thereof and Producing Method Thereof | |
| JPH0214866A (en) | Solution of calcium phosphate compound ceramic precursor and production thereof | |
| JP2014506812A (en) | Composition containing injectable self-hardening apatite cement | |
| CN108424138A (en) | Siliceous modified grain boundary phase hydroxylapatite ceramic, bone injury repair material and preparation method thereof | |
| CN107412874B (en) | Injectable calcium sulfate hemihydrate/octacalcium phosphate/sodium hyaluronate sulfate composite artificial bone material and preparation method thereof | |
| JP6414949B2 (en) | Self-curing chitosan-containing calcium phosphate composition, kit for producing the composition, and production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |