CN113616852A - Magnesium powder/calcium phosphate composite bone cement material and preparation method thereof - Google Patents
Magnesium powder/calcium phosphate composite bone cement material and preparation method thereof Download PDFInfo
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- CN113616852A CN113616852A CN202110978376.XA CN202110978376A CN113616852A CN 113616852 A CN113616852 A CN 113616852A CN 202110978376 A CN202110978376 A CN 202110978376A CN 113616852 A CN113616852 A CN 113616852A
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- magnesium powder
- bone cement
- calcium phosphate
- powder
- phosphate
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 77
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 77
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 70
- 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 70
- 239000002639 bone cement Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000007790 solid phase Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims abstract description 12
- 235000019796 monopotassium phosphate Nutrition 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 9
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 9
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- NFIYTPYOYDDLGO-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].OP(O)(O)=O NFIYTPYOYDDLGO-UHFFFAOYSA-N 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 11
- 210000000988 bone and bone Anatomy 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000004071 biological effect Effects 0.000 abstract description 4
- 230000017423 tissue regeneration Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 abstract description 2
- 239000004137 magnesium phosphate Substances 0.000 abstract 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 abstract 1
- 229960002261 magnesium phosphate Drugs 0.000 abstract 1
- 235000010994 magnesium phosphates Nutrition 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 33
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 7
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 230000021164 cell adhesion Effects 0.000 description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 206010017076 Fracture Diseases 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 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 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012890 simulated body fluid Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000024779 Comminuted Fractures Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012227 artificial bone substitute Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000010478 bone regeneration Effects 0.000 description 1
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- YQRTZUSEPDULET-UHFFFAOYSA-K magnesium;potassium;phosphate Chemical group [Mg+2].[K+].[O-]P([O-])([O-])=O YQRTZUSEPDULET-UHFFFAOYSA-K 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000009818 osteogenic differentiation Effects 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
-
- 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
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- 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
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
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Abstract
The invention relates to a magnesium powder/calcium phosphate composite bone cement material and a preparation method thereof, which adopts phosphate solution to coat magnesium powder, successfully prepares a magnesium phosphate coating on the surface of the magnesium powder, and the coating can inhibit the over-fast reaction with acid curing liquid, thereby preparing a novel magnesium powder/calcium phosphate composite bone cement on the basis of not influencing the performance of calcium phosphate bone cement. The composite bone cement consists of a solid phase and a liquid phase, wherein the solid phase is formed by mixing calcium phosphate powder and coated magnesium powder according to a weight ratio, the added mass of the magnesium powder accounts for 0.01-20 w.t% of the total solid, the liquid phase is a mixed aqueous solution of 1mol/L potassium dihydrogen phosphate and dipotassium hydrogen phosphate, and the liquid-solid ratio is 0.2-0.5 mL/g. The prepared composite bone cement has good mechanical property, faster degradation rate and better biological activity, and has wide application prospect in the field of clinical bone tissue repair.
Description
Technical Field
The invention belongs to the field of biomedical materials and a preparation technology thereof, and relates to a magnesium powder/calcium phosphate composite bone cement material and a preparation method thereof.
Background
Unstable fractures such as osteoporosis-induced fractures, particularly comminuted fractures, frequently occur clinically with age. To solve the above problems, not only medical skill of doctors but also excellent bone repair materials are required. Calcium Phosphate Cement (CPC) is a novel self-setting artificial bone substitute material developed by Brown and Chow in the middle of the 80's 20 th century, and is currently widely used in clinic. CPC is a ceramic-based hydroxyapatite bone repair material with self-curing property, shape plasticity, good biocompatibility, micro-nano porous structure and injectability, thus the CPC is widely concerned in the medical field, is successfully applied to the treatment of bone defects and fractures, and has wide application prospect.
From the clinical application point of view, however, there are still some problems to be solved with CPC [ r. krueger, Biomaterials,33(25) (2012), 5887-; lee, Mater Sci Eng C Mater Biol Appl,94(2019),385- "392": the CPC has insufficient mechanical property and cannot be used for repairing bone tissues of a bearing part; CPC degrades slowly and cannot provide space for the growth of new bones in time; CPC has a weak capacity to promote osteogenic differentiation and lacks osteogenic inducing ability. Therefore, how to improve the strength of the CPC and accelerate the degradation of the CPC has important significance for clinical application of the CPC.
Recent research shows that the magnesium-based material has excellent mechanical properties similar to human bones, biodegradability and biocompatibility, and has excellent properties of promoting osteogenesis, influencing bone regeneration, accelerating repair process and the like. The magnesium powder is taken as a new generation of spherical filler in the magnesium-based material, not only can play a role in bearing, but also can promote the degradation performance [ Q.Zhai, int.J.mol.Sci,19(6) (2018) ]. In addition, the degradation process of magnesium powder can form macropores in situ, which can accelerate the degradation of cement. Compared with other spherical pore-forming agents such as gelatin, the degradation of magnesium powder can increase the alkalinity of the surrounding environment, contribute to the formation of hydroxyapatite products and reduce the occurrence of inflammatory reaction [ J.Walker, J.BIOMED MATER RES B,102(6) (2014),1316-1331 ]. Notably, the degradation rate of magnesium-based materials in vivo is too fast, limiting their widespread clinical use. The coating is one of effective methods for improving the corrosion resistance of the magnesium alloy. Currently, the modification of magnesium and magnesium alloys includes bulk modification and surface modification [ Hornberger H, Acta Biomater,8(7) (2012), 2442-. The most widely applied is surface coating modification, and various coatings can be prepared, such as metal phosphate coatings, calcium-phosphorus coatings, fluorine-containing functional coatings, organic coatings and the like.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a magnesium powder/calcium phosphate composite bone cement material and a preparation method thereof.
Technical scheme
The magnesium powder/calcium phosphate composite bone cement material is characterized in that: adding magnesium powder into the calcium phosphate cement to form composite bone cement, wherein the addition amount of the magnesium powder accounts for 0.01-20 wt% of the mass fraction of the calcium phosphate cement; the magnesium powder is treated by adopting the surface of phosphate to form a surface coating containing phosphoric acid.
The phosphate salts include, but are not limited to: dipotassium phosphate solution, potassium phosphate solution, disodium phosphate solution or sodium dihydrogen phosphate solution.
The particle size of the magnesium powder is 50-300 mu m.
The purity of the magnesium powder is not lower than 99%.
A method for preparing the magnesium powder/calcium phosphate composite bone cement material is characterized by comprising the following steps:
step 1, magnesium powder coating pretreatment: preparing 100mL of 0.1-0.3 mol/L phosphate aqueous solution, adding 2-5 g of magnesium powder while magnetically stirring, reacting for 3-24h, removing turbid liquid on the upper layer of the reaction mixture, directly washing the bottom layer precipitate with deionized water for multiple times, drying at low temperature, and storing the obtained coated magnesium powder at normal temperature in vacuum;
The magnetic stirring speed is 200-400 rpm.
And directly washing the bottom layer precipitate for 3-5 times by using deionized water.
Preparation of the calcium phosphate cement powder: taking tetracalcium phosphate and calcium hydrogen phosphate powder with a molar ratio of 1:1, putting the tetracalcium phosphate and the calcium hydrogen phosphate powder into a ball mill, wet-milling the tetracalcium phosphate and the calcium hydrogen phosphate powder by using absolute ethyl alcohol as a solvent, wherein the ball milling rotation speed is 300-500rpm, the ball milling time is 12-24h, uniformly mixing, pouring out the slurry, and drying the slurry in a forced air drying box at 80 ℃ for 12h to obtain the tetracalcium phosphate and calcium hydrogen phosphate powder.
Advantageous effects
The magnesium powder/calcium phosphate composite bone cement material and the preparation method provided by the invention have the advantages that the magnesium powder is coated by the phosphate solution, the magnesium phosphate salt coating is successfully prepared on the surface of the magnesium powder, and the coating can inhibit the over-fast reaction with the acidic curing liquid, so that the novel magnesium powder/calcium phosphate composite bone cement is prepared on the basis of not influencing the performance of the calcium phosphate bone cement. The composite bone cement consists of a solid phase and a liquid phase, wherein the solid phase is formed by mixing calcium phosphate powder and coated magnesium powder according to a weight ratio, the added mass of the magnesium powder accounts for 0.01-20 w.t% of the total solid, the liquid phase is a mixed aqueous solution of 1mol/L potassium dihydrogen phosphate and dipotassium hydrogen phosphate, and the liquid-solid ratio is 0.2-0.5 mL/g. The prepared composite bone cement has good mechanical property, faster degradation rate and better biological activity, and has wide application prospect in the field of clinical bone tissue repair.
Compared with the prior art, the invention has the beneficial effects that:
1. the magnesium powder/calcium phosphate composite bone cement can be formed into paste after being blended and then solidified into a block-shaped filler, and can be used for filling bone defects.
2. The invention combines the magnesium powder material with high degradation rate and good biological activity with calcium phosphate cement, and solves the problem of low mechanical strength caused by the over-high reaction rate of pure magnesium powder and curing liquid.
The invention improves the compressive strength of the composite bone cement, improves the degradation performance and the biological activity of the material, and is more expected to be applied to the field of bone tissue repair.
Drawings
FIG. 1: scanning photograph of magnesium powder surface: (a) original magnesium powder, (b) processing for 6h, (c) processing for 12h, and (d) processing for 24 h;
FIG. 2: the XRD pattern of the untreated magnesium powder surface and the XRD pattern after 12 hours of treatment;
FIG. 3: the surface appearance of the magnesium powder and calcium phosphate cement after being compounded is as follows: (a) untreated magnesium powder composite calcium phosphate cement, (b) pure calcium phosphate cement, (c) treated 5 wt.% magnesium powder composite calcium phosphate cement, (d) treated 10 wt.% magnesium powder composite calcium phosphate cement;
FIG. 4: adding the compressive strength of the composite of the treated magnesium powder and the calcium phosphate cement with different contents and different treatment times, wherein the composite of the untreated magnesium powder and the calcium phosphate cement is used as comparison data;
FIG. 5: the in vitro degradation rate and the pH value of the magnesium powder composite calcium phosphate bone cement and the pure calcium phosphate bone cement are compared at different time points;
FIG. 6: scanning the cell adhesion morphology of the pure calcium phosphate cement and the treated magnesium powder composite calcium phosphate cement;
FIG. 7: magnesium powder/calcium phosphate bone cement preparation process.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the first embodiment is as follows:
the method comprises the following steps: surface treatment of magnesium powder
First, 100mL of 0.1mol/L KH was prepared2PO4The aqueous solution was then weighed 2g of magnesium powder with a diameter of about 50 μm and slowly added to KH under rapid magnetic stirring (400rpm)2PO4Treating the magnesium powder in the aqueous solution for 6 hours. After the reaction was completed, the upper layer of the reaction mixture was removed. The coated powder is stored after drying for further use. The XRD pattern shows that the main component of the surface coating after treatment is magnesium potassium phosphate.
The KH2PO4The aqueous solution can be prepared from dipotassium hydrogen phosphate solution, potassium dihydrogen phosphate solution, disodium hydrogen phosphate solution or sodium dihydrogen phosphate solutionLiquid substitution
Step two: preparation of calcium phosphate bone cement
The tetracalcium phosphate powder and the calcium hydrogen phosphate powder with the molar ratio of 1:1 are put into a planetary ball mill, the wet milling is carried out by taking absolute ethyl alcohol as a solvent, the ball milling speed is 300rpm, the ball milling time is 12 hours, after the uniform mixing, the slurry is poured out and is placed in an air-blast drying oven at the temperature of 80 ℃ for drying for 12 hours.
Step three: preparation of magnesium powder-calcium phosphate composite bone cement
And uniformly mixing the magnesium powder after 6 hours of treatment into the calcium phosphate cement powder according to 5 wt.% of the total mass of the solid-phase powder to obtain the composite bone cement solid-phase powder. Taking a mixed aqueous solution of 1mol/L potassium dihydrogen phosphate and dipotassium hydrogen phosphate as a liquid phase, and uniformly mixing powder and liquid with the liquid-solid ratio of 0.4 mL/g. And (3) placing the mixed paste into a polytetrafluoroethylene mold, curing, taking out, and demolding to obtain a mechanical property sample (phi 6 x 10 mm). The compressive strength after three days of hydration is about 10MPa, which shows that the mechanical property of the composite bone cement is not reduced by adding the coated magnesium powder after 6 hours of treatment.
Example two:
the method comprises the following steps: surface treatment of magnesium powder
Similar to example one, the only difference is that the treatment time is extended from 6h to 12 h.
Step two: preparation of calcium phosphate bone cement
The same as in example one.
Step three: preparation of magnesium powder-calcium phosphate composite bone cement
And uniformly mixing the magnesium powder after 12 hours of treatment into the calcium phosphate cement powder according to 5 wt.% of the total mass of the solid-phase powder to obtain the composite bone cement solid-phase powder. Taking a mixed aqueous solution of 1mol/L potassium dihydrogen phosphate and dipotassium hydrogen phosphate as a liquid phase, and uniformly mixing powder and liquid with the liquid-solid ratio of 0.4 mL/g. And (3) placing the mixed paste into a polytetrafluoroethylene mold, curing, taking out, and demolding to obtain a mechanical property sample (phi 6 x 10 mm). The compressive strength after three days of hydration is about 13MPa, which shows that the mechanical property of the composite bone cement can be improved by prolonging the treatment time of the magnesium powder.
Example three:
the method comprises the following steps: surface treatment of magnesium powder
Similar to example one, the only difference is that the treatment time is extended from 6h to 24 h.
Step two: preparation of calcium phosphate bone cement
The same as in example one.
Step three: preparation of magnesium powder-calcium phosphate composite bone cement
And uniformly mixing the magnesium powder after 24 hours of treatment into the calcium phosphate cement powder according to 5 wt.% of the total mass of the solid-phase powder to obtain the composite bone cement solid-phase powder. Taking a mixed aqueous solution of 1mol/L potassium dihydrogen phosphate and dipotassium hydrogen phosphate as a liquid phase, and uniformly mixing powder and liquid with the liquid-solid ratio of 0.4 mL/g. And (3) placing the mixed paste into a polytetrafluoroethylene mold, curing, taking out, and demolding to obtain a mechanical property sample (phi 6 x 10 mm). The compressive strength after three days of hydration is about 6MPa, which indicates that the excessive treatment time of the magnesium powder can cause the coating to lose efficacy, thereby affecting the mechanical properties of the composite bone cement.
Example four:
the method comprises the following steps: surface treatment of magnesium powder
The same as in example one.
Step two: preparation of calcium phosphate bone cement
The same as in example one.
Step three: preparation of magnesium powder-calcium phosphate composite bone cement
And uniformly mixing the magnesium powder after 6 hours of treatment into the calcium phosphate cement powder according to 10 wt.% of the total mass of the solid-phase powder to obtain the composite bone cement solid-phase powder. Taking a mixed aqueous solution of 1mol/L potassium dihydrogen phosphate and dipotassium hydrogen phosphate as a liquid phase, uniformly mixing powder and liquid with a liquid-solid ratio of 0.4mL/g, co-culturing 10 wt.% of coated magnesium powder calcium phosphate bone cement and MC3T3-E1 cells, and observing the cell adhesion condition, wherein compared with pure CPC, the 10 wt.% of coated magnesium powder calcium phosphate bone cement has more complete cell spreading on the surface, namely the coated magnesium powder calcium phosphate bone cement has better affinity to the cells.
Example five:
the method comprises the following steps: surface treatment of magnesium powder
The same as in example two.
Step two: preparation of calcium phosphate bone cement
The same as in example one.
Step three: preparation of magnesium powder-calcium phosphate composite bone cement
And uniformly mixing the magnesium powder after 12 hours of treatment into the calcium phosphate cement powder according to 10 wt.% of the total mass of the solid-phase powder to obtain the composite bone cement solid-phase powder. Taking a mixed aqueous solution of 1mol/L potassium dihydrogen phosphate and dipotassium hydrogen phosphate as a liquid phase, uniformly mixing powder and liquid with the liquid-solid ratio of 0.4mL/g, preparing the mixed paste into a sample with the size of phi 6 x 10mm, curing for one day, and then placing the sample in a simulated body fluid at 37 ℃ and in a 100% environment for an explanation experiment. The data indicate that 10 wt.% of the coated powdered magnesium calcium phosphate cement degrades faster than pure calcium phosphate cement, and its pH is also higher than pure bone cement, showing excellent degradation properties.
Comparative example:
preparing pure calcium phosphate bone cement:
the method comprises the following steps: putting tetracalcium phosphate and calcium hydrogen phosphate powder with a molar ratio of 1:1 equal to that of the tetracalcium phosphate and the calcium hydrogen phosphate powder into a planetary ball mill, wet-milling the tetracalcium phosphate and the calcium hydrogen phosphate powder by using absolute ethyl alcohol as a solvent, wherein the ball-milling speed is 300rpm, the ball-milling time is 12 hours, pouring out the slurry after uniform mixing, and drying the slurry in a blast drying oven at 80 ℃ for 12 hours;
step two: taking 1moL/l of mixed aqueous solution of monopotassium phosphate and dipotassium phosphate as liquid phase, uniformly mixing powder and liquid with the liquid-solid ratio of 0.4mL/g, and blending to obtain paste, namely the calcium phosphate cement.
And (3) placing the mixed paste into a polytetrafluoroethylene mold, curing, taking out, and demolding to obtain a mechanical property sample (phi 6 x 10 mm). The compressive strength after three days of hydration was about 8.5MPa, indicating that the mechanical properties of pure calcium phosphate cements are lower than 5 wt.% magnesium coated calcium phosphate cements.
The paste after blending is made into a sample with the size of phi 6 x 10mm, and the sample is placed in simulated body fluid at 37 ℃ and in a 100% environment for explanation experiments after being solidified for one day. The data indicate that pure calcium phosphate cement degrades the slowest and its pH is the lowest. When the pure calcium phosphate cement and MC3T3-E1 cells were cultured together, cell adhesion was observed, cell adhesion and spreading were good, but the effect was not as good as that of 5 wt.% coated magnesium powder calcium phosphate cement.
② preparation of untreated magnesium powder-calcium phosphate composite bone cement
The method comprises the following steps: same as in comparative example one
Step two: magnesium powder is not processed;
step three: taking 1moL/l of mixed aqueous solution of monopotassium phosphate and dipotassium phosphate as liquid phase, uniformly mixing powder and liquid with the liquid-solid ratio of 0.4mL/g, and blending to obtain paste, namely the comparative magnesium powder calcium phosphate composite bone cement.
And (3) placing the mixed paste into a polytetrafluoroethylene mold, curing, taking out, and demolding to obtain a mechanical property sample (phi 6 x 10 mm). The compressive strength after three days of hydration is about 2MPa, which shows that the mechanical property of the pure magnesium composite calcium phosphate cement is the lowest. The observation of a scanning electron microscope shows that the surface of the pure magnesium composite calcium phosphate cement has large holes, which are generated by gas released by the reaction of magnesium powder and an acid curing liquid, while the surface of the coated magnesium powder composite calcium phosphate cement is compact, and no atmospheric hole is observed.
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| CN115444967A (en) * | 2022-08-08 | 2022-12-09 | 武汉理工大学 | Bioactive hard tissue adhesive and preparation method and application thereof |
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