CN106693063B - A kind of anti-collapsibility calcium silicon substrate composite bone cement and its preparation method and application - Google Patents

A kind of anti-collapsibility calcium silicon substrate composite bone cement and its preparation method and application Download PDF

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CN106693063B
CN106693063B CN201510797255.XA CN201510797255A CN106693063B CN 106693063 B CN106693063 B CN 106693063B CN 201510797255 A CN201510797255 A CN 201510797255A CN 106693063 B CN106693063 B CN 106693063B
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bone cement
sodium alginate
silicon substrate
composite bone
calcium
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CN106693063A (en
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常江
徐晨
郇志广
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Shanghai Institute of Ceramics of CAS
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    • 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
    • A61L27/52—Hydrogels or hydrocolloids
    • 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
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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
    • A61L27/14—Macromolecular materials
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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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/06—Flowable or injectable implant compositions
    • 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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Abstract

The present invention relates to a kind of anti-collapsibility calcium silicon substrate composite bone cements and its preparation method and application, the calcium silicon substrate composite bone cement is reconciled to obtain by Solid raw materials and liquid phase feed according to the ratio that liquid-solid ratio is 0.4 ~ 1.2 mL/g, wherein, the Solid raw materials are calcium silica-base material, and the liquid phase feed is sodium alginate soln.The present invention utilizes the characteristic of calcium silicon substrate bone cement and sodium alginate, prepares the calcium silicon substrate bioactive bone cement of novel injectable, preparation method is simple.The composite bone cement material has excellent syringeability, plasticity and anti-collapsibility, is suitable for the purposes such as dentistry, orthopaedics.

Description

A kind of anti-collapsibility calcium silicon substrate composite bone cement and its preparation method and application
Technical field
The invention belongs to biomaterial for medical purpose fields, are related to a kind of calcium silicon substrate composite bone cement material with anti-collapsibility performance Material and its preparation method and application.The syringeability material can be used for dentistry, orthopaedics as human body hard tissue filling renovation material Etc. purposes.
Background technique
Bone defect is the most common disease in orthopaedics, needs a large amount of bone renovating material to cure and repair, therefore is developed The various bio-medical materials for being suitable for defect of human body bone reparation have important social effect.It is led in inorganic bone renovating material Domain, compared to block-like bioceramic material, self-curing material because its with low-temperature setting, injectable, can be according to bone defect portion Special performance (the Journal of the Ceramic Society of Japan1991 of the shape random-shaping of position；99: It 954-64) receives extensive attention and applies.
Currently, the inorganic-bone cement in clinical application mainly includes calcium sulfate (Calcium Sulfate Cement, CSC) (Journal of Inorganic Materials2013；28:795-803), calcium phosphate (Calcium Phosphate Cement,CPC)(Journal of Applied Biomaterials&Functional Materials 2012；10:2- 11) etc., but there is shortage bioactivity (Journal of Materials Science-Materials in traditional bone cement in Medicine2013；24:355-64), degradation speed and ostosis speed mismatch (Acta Biomaterialia 2014；10:3279-87；Journal of Spinal Disorders&Techniques 2012；25:333-7) the problems such as. Therefore, Bone Colonizable Cements In Rabbits system is developed to have a very important significance.Studies have shown that with tricalcium silicate (Ca3SiO5) (Journal of Biomedical Materials Research Part A2008；85A:336-44), dicalcium silicate (Ca2SiO4)(Journal of Biomedical Materials Research Part B-Applied Biomaterials 2005；After 73B:244-51) being reconciled for the new calcium silicon substrate bone cement of representative and water the cement slurry that is formed have voluntarily solidification, The characteristics of random-shaping, and the system bone cement has good bioactivity and degradability, dissolves out in degradation process Silicon ion can promote osteoblastic proliferation and differentiation (Journal of Materials Chemistry2009；19:1183； Journal of Dentistry 2014；42:517-33).But calcium silicon substrate bone cement there are anti-collapsibilities poor, setting time Long, a series of problem such as mechanical strength is relatively low, and serious separation of solid and liquid phenomenon can be generated in injection process.Liu et al. People (International Journal of Applied Ceramic Technology 2011；8:560-565) by silicic acid Tricalcium (C3S), dicalcium silicate (C2S) two kinds of powders are compound, by regulate and control the ratios of two kinds of powders to the physicochemical property of bone cement into The a series of regulation of row, and can effectively shorten bone cement setting time, improve the compression strength of bone cement.However these Work the disadvantage that can not still overcome calcium silicon substrate bone cement intrinsic, this will lead to bone cement and is easy to be broken up by blood in the application, In The problems such as serious separation of solid and liquid is generated in injection process.Therefore, developing one kind not only has bioactivity but also has excellent resist Collapsibility, injectable/shaping Bone Colonizable Cements In Rabbits are very necessary.
Summary of the invention
For the disadvantages described above of the prior art, the purpose of the present invention is to provide a kind of calcium silicon with anti-collapsibility characteristic Base composite bone cement.Wherein calcium silicon substrate bone cement can voluntarily solidify, and the system bone cement has good bioactivity And degradability, the silicon dissolved out in degradation process (Si) ion can promote osteoblastic proliferation and differentiation；Sodium alginate (SA) meeting Same calcium (Ca) ionic reaction generates calcium alginate hydrogel, effectively inhibits the defeated and dispersed of calcium silicon substrate bone cement.
Here, the present invention provides a kind of anti-collapsibility calcium silicon substrate composite bone cement, the calcium silicon substrate composite bone cement is by solid phase Raw material and liquid phase feed reconcile to obtain according to the ratio that liquid-solid ratio is 0.4~1.2mL/g, wherein the Solid raw materials are calcium silicon Sill, the liquid phase feed are sodium alginate soln.
The material is formed using biologically active calcium silicon substrate bone cement powder as solid phase, with sodium alginate (Sodium Alginate, SA) solution be distiller liquor, through reconcile uniformly after formed.The present invention utilizes calcium silicon substrate bone cement and sodium alginate Characteristic, prepares the calcium silicon substrate bioactive bone cement of novel injectable, and preparation method is simple.Composite bone cement material tool There are excellent syringeability, plasticity and anti-collapsibility, is suitable for the purposes such as dentistry, orthopaedics.Its syringeability, it is shapeable, The performances such as setting time and mechanical strength can be regulated and controled by adjusting composition.In addition, composite material also has good life Object activity and regulatable degradation property, and can support the proliferation and differentiation of related osteoblast.The present invention has preparation The advantages that prepare with scale simple for process, low in cost, easy.
Preferably, the composition of the calcium silica-base material are as follows: tricalcium silicate (Ca3SiO5, C3S), dicalcium silicate (Ca2SiO4, C2) or tricalcium silicate/dicalcium silicate (Ca S3SiO5/Ca2SiO4, C3S/C2S) mixed powder, silicic acid three in calcium silicon substrate mixed powder Calcium (C3S) content of powder is 0~100%, dicalcium silicate (C2S) content of powder is 0~100%.
Preferably, the partial size of tricalcium silicate powder is 1~100 μm, dicalcium silicate diameter of particle is 1~100 μm.
Preferably, the sodium alginate soln is sodium alginate aqueous solution, concentration is 0.1wt%~10wt%.
Preferably, the molecular weight of sodium alginate is 5000~200000.
Calcium silicon substrate composite bone cement of the invention has following one or more features:
Anti-collapsibility performance: injection water in do not occur it is defeated and dispersed (by composite bone cement slurry inject deionized water in, do not have defeated and dispersed Phenomenon occurs), after being placed in concussion in 120r/ minutes 24 hours, the weight-loss ratio of composite bone cement slurry is less than 5%；
Setting time: the presetting period is 20~80 minutes, and final setting time is 30~180 minutes；
Syringeability energy: injectable rate is 90~100% after standing 5~30 minutes；
Compression strength: after maintenance 28 days, compression strength is greater than 20MPa, preferably 20~60MPa, more preferable 50MPa or more.
Another object of the present invention is to provide a kind of preparation methods of calcium silicon substrate composite bone cement, which is characterized in that institute Stating preparation method includes: the ratio tune for being 0.4~1.2mL/g according to liquid-solid ratio by calcium silica-base material powder and sodium alginate soln With obtain the calcium silicon substrate/sodium alginate composite bone cement with anti-collapsibility property.
Preferably, the sodium alginate soln is added to the water by sodium alginate powder, stirs preparation in 1~5 hour and obtain, institute The concentration for stating sodium alginate soln is 0.1wt%~10wt%, and the molecular weight of sodium alginate is 5000~200000.
Preferably, the calcium silica-base material powder is tricalcium silicate, dicalcium silicate or tricalcium silicate/dicalcium silicate mixed powder Body, wherein the partial size of tricalcium silicate powder is 1~100 μm, and dicalcium silicate diameter of particle is 1~100 μm.
The object of the invention is also to provide above-mentioned calcium silicon substrate composite bone cement in preparation for minimally-invasive treatment or complicated bone Application in the material of the filling of defect shape.The composite bone cement material has excellent anti-collapsibility, syringeability or can Plasticity is suitable for the purposes such as dentistry, orthopaedics.
Detailed description of the invention
Fig. 1 is that (calcium silica-base material is in this figure for XRD spectrum after calcium silicon substrate/sodium alginate composite bone cement conserves 14 days Tricalcium silicate powder, liquid-solid ratio 0.6mL/g).(a) tricalcium silicate；(b) distiller liquor is 1.0% sodium alginate soln；(c) it adjusts It is 1.5% sodium alginate soln with liquid；(d) distiller liquor be 2.0% sodium alginate soln (◆: C-S-H；*: C3S；O:Ca (OH)2)。
Fig. 2 is cross-section morphology figure (the calcium silica-base material in this figure after calcium silicon substrate/sodium alginate composite bone cement conserves 14 days For tricalcium silicate powder, liquid-solid ratio 0.6mL/g).(a) tricalcium silicate；(b) distiller liquor is 1.0% sodium alginate soln；(c) Distiller liquor is 1.5% sodium alginate soln；(d) distiller liquor is 2.0% sodium alginate soln.
Fig. 3 is that calcium silicon substrate/sodium alginate composite bone cement anti-collapsibility compares figure (calcium silica-base material is silicic acid in this figure Tricalcium powder, liquid-solid ratio 0.6mL/g).(a) tricalcium silicate；(b) distiller liquor is 1.0% sodium alginate soln；(c) distiller liquor For 1.5% sodium alginate soln；(d) distiller liquor is 2.0% sodium alginate soln.
Fig. 4 is that calcium silicon substrate/sodium alginate composite bone cement syringeability compares figure (calcium silica-base material is silicic acid in this figure Tricalcium powder, liquid-solid ratio 0.6mL/g).
Fig. 5 is that (calcium silica-base material is tricalcium silicate powder to calcium silicon substrate/sodium alginate composite bone cement plasticity figure in this figure Body, liquid-solid ratio 0.6mL/g).
Fig. 6 is that (calcium silica-base material is tricalcium silicate to calcium silicon substrate/sodium alginate composite bone cement curing time figure in this figure Powder, liquid-solid ratio 0.6mL/g).
Fig. 7 is that (calcium silica-base material is tricalcium silicate to calcium silicon substrate/sodium alginate composite bone cement compression strength figure in this figure Powder, liquid-solid ratio 0.6mL/g).
Fig. 8 is that calcium silicon substrate/sodium alginate composite bone cement impregnates 14 days rear surface patterns and EDS figure (in this figure in SBF Calcium silica-base material is tricalcium silicate powder, liquid-solid ratio 0.6mL/g).(a) tricalcium silicate；(b) distiller liquor is 1.5% alginic acid Sodium solution.
Fig. 9 is that (calcium silica-base material is tricalcium silicate powder to calcium silicon substrate/sodium alginate composite bone cement degradability figure in this figure Body, liquid-solid ratio 0.6mL/g).
Figure 10 is that (calcium silica-base material is silicon to calcium silicon substrate/sodium alginate composite bone cement cell compatibility figure in this figure Sour tricalcium powder, liquid-solid ratio 0.6mL/g).
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for Illustrate the present invention, is not intended to limit the present invention.
In the present invention, based on biologically active calcium silicon substrate bone cement, it is excellent that biocompatibility is introduced thereto Macromolecule, it is final wish to obtain anti-collapsibility, syringeability it is excellent or can random-shaping composite bone cement slurry.The present invention The macromolecule of middle selection be sodium alginate (SA), reason be natural polymer sodium alginate (SA) have retentiveness, hypotoxicity, Biocompatibility, it is sequestering the features such as, wound dressing, drug and in terms of be widely used (Progress in Polymer Science 2012；37:106-2).With calcium (Ca) ion chela can occur for sodium alginate (SA) It closes reaction and generates the calcium alginate hydrogel with anti-collapsibility, and calcium silicon substrate bone cement ingredient forms C-S-H network in aquation Calcium (Ca) ion can be constantly discharged during structure.Therefore we discharge calcium based on calcium silicon substrate bone cement in hydration process (Ca) characteristic of ion combines it with the characteristic of sodium alginate (SA), and being formed has the new calcium silicon substrate of anti-collapsibility multiple Close bone cement.
Anti-collapsibility calcium silicon substrate composite bone cement material of the invention, Solid raw materials are the calcium silicon substrate with self-curing performance Material, liquid phase feed are sodium alginate (SA) solution, and for the two after homogeneous modulation mixes, being formed has anti-collapsibility performance, injectable Or the self-curing bone cement slurry of shaping.
The preparation method of anti-collapsibility calcium silicon substrate composite bone cement of the invention specifically includes following steps.
(1) sodium alginate soln
Sodium alginate (SA) powder of different quality is weighed respectively, is added in deionized water, and it is small to stir 1~5 at room temperature When, obtain sodium alginate (SA) solution of various concentration.In the present invention, the concentration of sodium alginate (SA) solution can be 0.1wt% ~10wt%, preferably 1wt%~2wt%.It wouldn't be in use, sodium alginate soln can be saved backup in low temperature environment, example 4 DEG C of refrigerators are such as placed in save.
(2) preparation of calcium silicon substrate composite bone cement
By sodium alginate (SA) solution of calcium silicon substrate bone cement powder and various concentration according to liquid-solid ratio be 0.4~1.2mL/ The ratio of g sufficiently reconciles 0.5~1 minute, obtains the calcium silicon substrate with anti-collapsibility property/sodium alginate composite bone cement slurry. When the liquid-solid ratio of calcium silicon substrate bone cement powder and sodium alginate (SA) solution exceeds above range, it will powder occur cannot consolidate The negative consequences such as change or curing time are too long.The calcium silicon substrate bone cement powder is preferably the calcium silicon substrate with self-curing performance Material, more preferably tricalcium silicate (Ca3SiO5, C3S), dicalcium silicate (Ca2SiO4, C2) or tricalcium silicate/dicalcium silicate S (Ca3SiO5/Ca2SiO4, C3S/C2S) mixed powder.The particle size range of tricalcium silicate powder can be 1~100 μm, dicalcium silicate powder Body particle size range can be 1~100 μm.As selection tricalcium silicate/dicalcium silicate (Ca3SiO5/Ca2SiO4, C3S/C2S) mixed powder When, the mass ratio of the two can be (0~100): (100~0), preferably (90~60): (10~40).
Above-mentioned bone cement slurry is conserved in 37 DEG C, the environment of 100% humidity.After maintenance 14 days, to bone cement product XRD and sem analysis are carried out, and makes performance evaluation.
Anti-collapsibility
Sodium alginate (SA) solution of various concentration is mixed with 0.4~1.2mL/g of liquid-solid ratio with calcium silicon substrate powder respectively, After mixing evenly, bone cement slurry is squeezed into manually in deionized water and observes the defeated and dispersed situation of slurry in water: simple calcium silicon Base bone cement is defeated and dispersed rapid in water；Composite bone cement slurry containing sodium alginate does not have defeated and dispersed phenomenon in water.It will Above-mentioned composite bone cement is placed in deionized water and after 120r/ minutes conditions is shaken 24 hours, the mistake of composite bone cement slurry For rate less than 5%, this illustrates that the composite bone cement has excellent anti-collapsibility again.
Syringeability and plasticity
Sodium alginate (SA) solution of various concentration is mixed with 0.4~1.2mL/g of liquid-solid ratio with calcium silicon substrate powder respectively, It stirs evenly, bone cement slurry is placed in syringe and stands 5 minutes, syringeability experiment is carried out to it；By bone cement slurry Any defect for pressing on mold carries out plasticity observation to it.Composite bone cement slurry of the present invention stands 5 points For injectable rate up to 90% or more, this illustrates that the composite bone cement has excellent syringeability, and bone cement slurry after clock It can be according to the shape random-shaping of defect during pressing.
Curing time and compression strength
Composite bone cement slurry is placed in Teflon mould (6 × 12mm of Ф3) in, 37 DEG C are placed in, 100% humidity Environment in conserve.Measure the presetting period and final setting time of several groups of slurries respectively with Vicat apparatus.In the system, pass through alginic acid The regulation of sodium (SA) content, the presetting period of composite bone cement and final setting time can be respectively at 40~60 minutes, 60~160 minutes Inside regulated and controled；After maintenance 28 days, compression strength can reach 20~60MPa.
Mineralization ability
Bioactivity survey is carried out using immersion test in simulated body fluid (SBF) to calcium silicon substrate/sodium alginate composite bone cement Examination, and SEM and EDS is carried out to the material face after immersion and is characterized.Calcium silicon substrate/sodium alginate composite bone cement provided by the invention The generation that osteoid apatite can be induced shows that the material has good bioactivity.
Degradability
External degradation test is carried out using Tri-HCl immersion test to calcium silicon substrate/sodium alginate composite bone cement.It can pass through The content of regulation sodium alginate (SA) regulates and controls the degradation rate of composite bone cement.
Cell compatibility
Body is carried out using osteoblast MC3T3 to calcium silicon substrate/sodium alginate composite bone cement leaching liquor after maintenance 3 days Outer cell compatibility experiment.The result shows that in the dilution of composite bone cement material leaching liquor, the ion energy obvious stimulation of dissolution The proliferation of MC3T3.
Beneficial effects of the present invention: anti-collapsibility calcium silicon substrate composite bone cement material of the invention has good anti-collapsibility Property, the performances such as syringeability, shapeable, setting time and mechanical strength can be regulated and controled by adjusting composition.In addition, Composite material also has good bioactivity and regulatable degradation property, and can support the proliferation of related osteoblast And differentiation.The present invention has many advantages, such as that preparation is simple, low in cost, easy prepare with scale.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
1) preparation of sodium alginate soln:
It weighs 0.2g sodium alginate powder to be dissolved in 20mL deionized water, and stirs evenly at room temperature, finally obtain Concentration is 1.0% sodium alginate soln, is placed in 4 DEG C of refrigerators and saves, spare；
2) tricalcium silicate/sodium alginate composite bone cement preparation:
Tricalcium silicate powder and 1.0% sodium alginate soln are reconciled uniformly with liquid-solid ratio 0.6mL/g, obtain silicic acid three Calcium/sodium alginate composite bone cement slurry, the content of sodium alginate is 0.6% at this time.In testing the Composite Bone under room temperature Anti-collapsibility, the syringeability of cement slurry.The result shows that the composite bone cement slurry in water obviously (join by anti-collapsibility effect See the figure b) in Fig. 3；Slurry stands injectable rate after five minutes in syringe and and injected close to 100% (referring to fig. 4) Without being separated by solid-liquid separation phenomenon in journey, illustrate that the composite bone cement slurry is suitable for the Minimally Invasive Surgery application of bone defect.Fig. 5 shows calcium Silicon substrate/sodium alginate composite bone cement plasticity, the composite bone cement has excellent plasticity as seen from Figure 5.By bone Cement slurry casting conserves under 37 DEG C, 100% damp condition, and the initial set of the composite bone cement is measured with Vicat apparatus And final setting time is respectively 57 minutes and 77 minutes (referring to Fig. 6).Fig. 7 shows the compression strength of the composite bone cement, can by Fig. 7 With find out maintenance 28 days after composite bone cement compression strength up to 55MPa.The composite bone cement piece is placed in SBF and impregnates 14 After it, SEM and EDS characterization (referring to Fig. 8) is carried out to the deposit on bone cement surface, the results showed that surface deposits are class bone phosphorus Lime stone, this illustrates that the composite bone cement can induce osteoid apatite mineralising.Fig. 9 shows the degradability of the composite bone cement, by Fig. 9 Weight-loss ratio is up to 55% after degradation after can be seen that one month of composite bone cement.Figure 10 shows the composite bone cement leaching liquor For the proliferation results of cultured osteoblast-like cells in vitro MC3T3, the composite bone cement has good cytocompatibility as seen from Figure 10 Property.
Embodiment 2
1) preparation of sodium alginate soln:
It weighs 0.3g sodium alginate powder to be dissolved in 20mL deionized water, and stirs evenly at room temperature, finally obtain Concentration is 1.5% sodium alginate soln, is placed in 4 DEG C of refrigerators and saves, spare；
2) tricalcium silicate/sodium alginate composite bone cement preparation:
Tricalcium silicate powder and 1.5% sodium alginate soln are reconciled uniformly with liquid-solid ratio 0.6mL/g, obtain silicic acid three Calcium/sodium alginate composite bone cement slurry, the content of sodium alginate is 0.9% at this time.In testing the Composite Bone under room temperature Anti-collapsibility, the syringeability of cement slurry.The result shows that the composite bone cement slurry in water obviously (join by anti-collapsibility effect See the figure c) in Fig. 3；Slurry stands injectable rate after five minutes in syringe and and injected close to 100% (referring to fig. 4) Without being separated by solid-liquid separation phenomenon in journey, illustrate that the composite bone cement slurry is suitable for the Minimally Invasive Surgery application of bone defect.By bone cement Slurry casting conserves under 37 DEG C, 100% damp condition, and initial set and the end of the composite bone cement are measured with Vicat apparatus The solidifying time is respectively 60 minutes and 89 minutes (referring to Fig. 6).Fig. 7 shows the compression strength of the composite bone cement, can be seen by Fig. 7 The compression strength of composite bone cement is up to 27.9MPa, for tricalcium silicate bone cement, the composite bone cement after conserving 28 days out Longtime compressive strength is slightly lower.The composite bone cement piece is placed in SBF after impregnating 14 days, the deposit on bone cement surface is carried out SEM and EDS characterization (referring to Fig. 8), the results showed that surface deposits are osteoid apatite, this illustrates that the composite bone cement can induce Osteoid apatite mineralising.Fig. 9 shows the degradability of the composite bone cement, as seen from Figure 9 behind one month of composite bone cement Degradation after weight-loss ratio up to 58%, higher than weight-loss ratio after the degradation of the composite bone cement in example 1.Figure 10 shows the Composite Bone Cement leaching liquor is used for the proliferation results of cultured osteoblast-like cells in vitro MC3T3, and the composite bone cement has good as seen from Figure 10 Cell compatibility.
Embodiment 3
1) preparation of sodium alginate soln:
It weighs 0.4g sodium alginate powder to be dissolved in 20mL deionized water, and stirs evenly at room temperature, finally obtain Concentration is 2.0% sodium alginate soln, is placed in 4 DEG C of refrigerators and saves, spare；
2) tricalcium silicate/sodium alginate composite bone cement preparation:
Tricalcium silicate powder and 2.0% sodium alginate soln are reconciled uniformly with liquid-solid ratio 0.6mL/g, obtain silicic acid three Calcium/sodium alginate composite bone cement slurry, the content of sodium alginate is 1.2% at this time.
Fig. 1 shows calcium silicon substrate made from tricalcium silicate and above-described embodiment 1~3/sodium alginate composite bone cement maintenance XRD spectrum after 14 days, the hydrated product of composite bone cement is not obvious with the hydrated product of tricalcium silicate as seen from Figure 1 Difference.Fig. 2 shows calcium silicon substrate made from tricalcium silicate and above-described embodiment 1~3/sodium alginate composite bone cements to conserve 14 days Cross-section morphology afterwards, sodium alginate produces bigger effect the cross-section morphology of composite bone cement as seen from Figure 2, wherein real The section structure applied in example 1 (shown in Fig. 2 b) is more fine and close.Fig. 3 shows calcium made from tricalcium silicate and above-described embodiment 1~3 Silicon substrate/sodium alginate composite bone cement anti-collapsibility, composite bone cement slurry of the invention resists in water as seen from Figure 3 Defeated and dispersed effect is obvious.Fig. 4 shows calcium silicon substrate/sodium alginate composite bone cement made from tricalcium silicate and above-described embodiment 1~3 Syringeability, as seen from Figure 4 relative to simple tricalcium silicate bone cement, the injectable rate of the composite bone cement reaches 90% or more, this illustrates that the composite bone cement has excellent syringeability.
Embodiment 4
1) preparation of sodium alginate soln:
It weighs 0.3g sodium alginate powder to be dissolved in 20mL deionized water, and stirs evenly at room temperature, finally obtain Concentration is 1.5% sodium alginate soln, is placed in 4 DEG C of refrigerators and saves, spare；
2) dicalcium silicate/sodium alginate composite bone cement preparation:
Dicalcium silicate powder and 1.5% sodium alginate soln are reconciled uniformly with liquid-solid ratio 0.5mL/g, obtain silicic acid two Calcium/sodium alginate composite bone cement slurry, the content of sodium alginate is 0.75% at this time.
In the anti-collapsibility of testing the composite bone cement slurry under room temperature and shapeable.The result shows that this is compound Anti-collapsibility effect is obvious in water for bone cement slurry；Defect bone model is made, composite bone cement slurry is pressed into lacking for model Position is damaged, bone cement slurry can be preferably bonded during cured with defect, illustrate the composite bone cement slurry It can filling according to the position random molding of bone defect, suitable for complicated shape bone defect position.
Embodiment 5
1) preparation of sodium alginate soln:
It weighs 0.4g sodium alginate powder to be dissolved in 20mL deionized water, and stirs evenly at room temperature, finally obtain Concentration is 2.0% sodium alginate soln, is placed in 4 DEG C of refrigerators and saves, spare；
2) tricalcium silicate/dicalcium silicate/sodium alginate composite bone cement preparation:
After mixing according to 4:1 by tricalcium silicate powder and dicalcium silicate powder, with 2.0% sodium alginate soln with liquid Gu reconciling uniformly than 0.6mL/g, tricalcium silicate/dicalcium silicate/sodium alginate composite bone cement slurry is obtained, at this time sodium alginate Content be 1.2%.
In anti-collapsibility, the syringeability of testing the composite bone cement slurry under room temperature.The result shows that the Composite Bone Anti-collapsibility effect is obvious in water for cement slurry；Slurry stood in syringe after five minutes injectable rate close to 100%, and Without being separated by solid-liquid separation phenomenon in injection process, illustrate that the composite bone cement slurry is suitable for the Minimally Invasive Surgery application of bone defect.It will Composite bone cement slurry casting tests its compression strength, composite bone cement after conserving under 37 DEG C, 100% damp condition Compression strength be obviously improved.
Embodiment 6
1) preparation of sodium alginate soln:
It weighs 0.4g sodium alginate powder to be dissolved in 20mL deionized water, and stirs evenly at room temperature, finally obtain Concentration is 2.0% sodium alginate soln, is placed in 4 DEG C of refrigerators and saves, spare；
2) tricalcium silicate/dicalcium silicate/sodium alginate composite bone cement preparation:
After mixing according to 4:1 by tricalcium silicate powder and dicalcium silicate powder, with 2.0% sodium alginate soln with liquid Gu reconciling uniformly than 0.5mL/g, tricalcium silicate/dicalcium silicate/sodium alginate composite bone cement slurry is obtained, at this time sodium alginate Content be 1.0%.
In the anti-collapsibility of testing the composite bone cement slurry under room temperature and shapeable.The result shows that this is compound Anti-collapsibility effect is obvious in water for bone cement slurry, and composite bone cement slurry can lack in the curing process with complicated shape Damage fitting illustrates that the composite bone cement slurry can be suitable for complicated shape bone defect according to the position random molding of bone defect The filling at position.
Industrial applicability: anti-collapsibility calcium silicon substrate composite bone cement material of the invention has excellent syringeability, plastic Property and anti-collapsibility, can be used for the filling of minimally-invasive treatment or complicated bone defect shape.

Claims (8)

1. a kind of anti-collapsibility calcium silicon substrate composite bone cement, which is characterized in that the calcium silicon substrate composite bone cement is by calcium silica-base material It reconciles to obtain according to the ratio that liquid-solid ratio is 0.4~1.2 mL/g with sodium alginate soln, wherein the sodium alginate soln is Sodium alginate aqueous solution, concentration are the wt of 0.1 wt%~10 %；The composition of the calcium silica-base material are as follows: tricalcium silicate, silicic acid two Calcium or tricalcium silicate/dicalcium silicate mixed powder.
2. calcium silicon substrate composite bone cement according to claim 1, which is characterized in that the partial size of tricalcium silicate powder be 1~ 100 μm, dicalcium silicate diameter of particle is 1~100 μm.
3. calcium silicon substrate composite bone cement according to claim 1, which is characterized in that the molecular weight of sodium alginate be 5000~ 200000。
4. calcium silicon substrate composite bone cement according to claim 1, which is characterized in that the calcium silicon substrate composite bone cement has Following one or more features:
Anti-collapsibility performance: injection water in do not occur it is defeated and dispersed, in 120r/ minute shake 24 hours after, the mistake of composite bone cement slurry Rate is less than 5% again；
Setting time: the presetting period is 20~80 minutes, and final setting time is 30~180 minutes；
Syringeability energy: injectable rate is 90~100% after standing 5~30 minutes；
Compression strength: after maintenance 28 days, compression strength is greater than 50 MPa.
5. a kind of preparation method of calcium silicon substrate composite bone cement described in any one of Claims 1-4, which is characterized in that institute Stating preparation method includes: the ratio for being 0.4~1.2 mL/g according to liquid-solid ratio by calcium silica-base material powder and sodium alginate soln It reconciles, obtains the calcium silicon substrate/sodium alginate composite bone cement with anti-collapsibility property.
6. preparation method according to claim 5, which is characterized in that the sodium alginate soln is added by sodium alginate powder Enter in water, stirs preparation in 1~5 hour and obtain, the concentration of the sodium alginate soln is the wt% of 0.1 wt%~10, sodium alginate Molecular weight be 5000~200000.
7. preparation method according to claim 5 or 6, which is characterized in that the calcium silica-base material powder be tricalcium silicate, Dicalcium silicate or tricalcium silicate/dicalcium silicate mixed powder, wherein the partial size of tricalcium silicate powder is 1~100 μm, silicic acid two Calcium diameter of particle is 1~100 μm.
8. a kind of calcium silicon substrate composite bone cement described in any one of Claims 1-4 is used for minimally-invasive treatment or complexity in preparation Application in the material of the filling of bone defect shape.
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