CN109432506A - A kind of high intensity injectable type bioactive materials and preparation method thereof - Google Patents
A kind of high intensity injectable type bioactive materials and preparation method thereof Download PDFInfo
- Publication number
- CN109432506A CN109432506A CN201811256583.9A CN201811256583A CN109432506A CN 109432506 A CN109432506 A CN 109432506A CN 201811256583 A CN201811256583 A CN 201811256583A CN 109432506 A CN109432506 A CN 109432506A
- Authority
- CN
- China
- Prior art keywords
- solidify liquid
- bioactive materials
- tricalcium silicate
- intensitive
- injectable type
- 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.)
- Pending
Links
Classifications
-
- 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
- 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
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
-
- 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
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
-
- 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
-
- 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
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Landscapes
- 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)
- Veterinary Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of high-intensitive injectable type bioactive materials, belong to biomedical materials field.Including nanometer grade silica, tricalcium silicate, solidify liquid；The mass ratio of tricalcium silicate powder, nanometer grade silica and solidify liquid is 1:0.01-0.05:0.4-0.8.The bioactive materials curing time is 30-55 minutes, and 7 days compression strength is 61-77 MPa, and can induce the formation of hydroxyapatite.Compared with current material, material of the invention has excellent in mechanical performance, and rapid curing has the characteristics such as superior bio activity.The invention also discloses a kind of preparation methods of high-intensitive injectable type bioactive materials.
Description
Technical field
The present invention relates to biomedical materials field, in particular to a kind of high-intensitive injectable type bioactive materials and its
Preparation method.
Background technique
In recent years, a large number of studies show that, some siliceous-calcium bioactive materials and calcium silicates bioceramic surface are in body
The inside and outside generation that can induce osteoid apatite, can promote biomaterial to be bonded with bone tissue.In addition, siliceous-calcium biology is living
Property material release silicon, calcium ion bone marrow stroma stem cell can be stimulated to osteoblast differentiation and active cell gene expression.
Tricalcium silicate (Tricalcium Silicate, TCS) is a kind of siliceous, calcium constituent bioactive materials, in people
In body bone tissue and the treatment of tooth defect repair, reparation can be filled in defect.Suitable solidify liquid is added in TCS powder
The paste of preparation has random-shaping, the features such as voluntarily solidification.It, can be in its table when TCS powder and simulated body fluid contact
Face forms nanoscale calcareous type bone like apatite layer.The calcareous type bone like apatite layer of the deposition has and nanometer in human body bone
The identical structure of the needle-shaped phosphorite crystal of grade is bonded and epitaxial growth to ensure that with the collagen in body bone tissue.
TCS is the main component of Portland cement, it is also dental filling material Mineral Trioxide
The main component of Aggregate (MTA, mineral trioxide aggregate), MTA is mainly by TCS, dicalcium silicate, tricalcium aluminate, iron
Four calcium of aluminic acid and bismuth oxide etc. are at being grouped as.It is invented by American scholar M. Torabinejad within MTA 1993, in nineteen ninety-five
It applies for a patent and starts selling.Approved by U.S. FDA within 1998, gradually widely accepted and controlling in pulpitis and periapical periodontitis
It is applied in treatment.MTA has good biocompatibility, bioactivity, biocidal property, low solubility, closure, X-ray resistance
Penetrating property etc. is applied to direct pulp capping, pulpotomia vitalis, pulp chamber perforation repairing, apexification, root-canal filling etc., still
This material above has some defects in application, this is mainly reflected in the following aspects: MTA curing time is longer, and one
As at 3-4 hours；The material easily makes tooth body change colour；MTA operating characteristics is poor etc..For solve MTA curing time it is longer the problems such as,
Domestic and foreign scholars have studied many for accelerating the cured additive of MTA, and wherein calcium chloride accelerates MTA solidification more obvious.
Wang etc. points out the chlorine of the addition 15% in TCS powder in research of the tricalcium silicate/calcium chloride complex cement for dental material
When changing calcium, final setting time was down to 90 minutes (Wang XH, Sun HC, Chang J. by 180 minutes
Characterization of Ca3SiO5/CaCl2 composite cement for dental application.
Dental Materials, 2008;24:74-82).When calcium chloride is added in TCS in the form of powder, composite granule is only
The mixing of micron order scale above can be reached, however, calcium chloride, which is previously dissolved in water phase solidify liquid, then may be implemented calcium chloride and water
Mud matrix uniformly mixes under smaller scale.
2009, novel TCS abutment essence alternative materials Biodentine was ground by French Sai Pudun (Septodont) company
It makes and is commercialized, which is exactly previously dissolved in calcium chloride in solidify liquid, and adds a certain amount of polycarboxylic acids in solidify liquid
Type water-reducing agent.More traditional MTA class dental material, Biodentine comprehensive performance are enhanced, and wherein curing time can
It is reduced to 45 minutes, 28 days compression strength is up to 67.18 MPa.(Grech L, Mallia B, Camilleri J.
Investigation of the physical properties of tricalcium silicate cement-based
root-end filling materials. Dental Materials, 2013;29:20-8).But face higher gear division
Clinical application technique requirement is repaired, Biodentine product still needs to improve in terms of curing time and compression strength.
In the 1990s, the application study of nano-particle material modified cement-concrete is increasingly becoming high performance silicon hydrochlorate
The research hotspot of gel rubber material.Existing research shows that adding a small amount of nano particle in cement concrete, can to improve its microcosmic
Structure improves its early strength.It, can be to 20-150 in hardening of cement slurry due to small 100 nm of the grain diameter of nano material
The micropore of nm plays filing effect, is effectively improved porosity and pore structure, so as to improve the mechanicalness of cement concrete
Energy.Be mainly nanometer miberal powder currently used for the nano material in cement concrete, as nanometer grade calcium carbonate, nano silica and
Nano-titanium dioxide etc., wherein nanometer silicon dioxide particle is that cement concrete improves a kind of more effective nanometer of comprehensive performance
Material.For existing level, the 7 days compression strength of cement concrete of 10% nanometer grade silica is added in 50 MPa or so.
In addition, size is small just because of " skin effect " specific to nanometer grade silica, surface can be high.With grain
Diameter reduces, and surface area, which sharply increases, causes surface atom number to increase sharply, thus surface atom has very high activity, extremely unstable
Fixed, Yi Fasheng agglomeration causes nano particle dispersion uneven；When nano particle dispersion is uneven, when agglomeration occurs,
Since the nano grain surface after reuniting has adsorbed more hydrone, the hydration reaction of cement matrix is hindered, it is suppressed that receive
The micro-packing effect and forming core of rice grain act on, and cause what the cement concrete comprehensive performance after solidifying occurred reducing instead to show
As.
For this problem, conventional cement concrete field mainly passes through addition dispersing agent, churned mechanically side at present
Method preparatory dispersing nanoparticles in water phase solve.Added dispersing agent includes polycarboxylic acids dehydragent.Ye etc. points out, when
In solidify liquid add 5% or so pre-add dispersing agents nanosized silica particles when, ordinary portland cement final setting time from
It is reduced within 263 minutes 186 minutes, 1 day intensity is increased to 53 MPa by 48.9 MPa.(Ye Q, Zhang Z, Kong D, et
al. Influence of nano-SiO2 addition on properties of hardened cement paste as
compared with silica fume. Construction & Building Materials, 2007; 21:539-
545.).
Although nanometer grade silica shows certain enhancing effect in terms of conventional cement concrete physical mechanical property
It answers, but nanometer grade silica is directly modified pure TCS and is applied to prepare syringeability bioactivity (especially gear division filling) material
When material, still it is difficult to sufficiently meet clinical application requirement in the improvement amplitude of intensity and curing time.
In addition, due to inorganic salts aquation accelerator in water dissociation energy release can strong acceleration of hydration ion, favorably
In compression double electric layer and Zeta-potential is reduced, therefore can promote to agglomerate.The nothings such as calcium chloride are added in high-performance water cement concrete
Machine salt aquation accelerator can change the state of charge of nano grain surface by its ion hydration in hydration process, interfere polycarboxylic acids
Class water-reducing agent is unfavorable for the raising of nano-particle reinforcement modified cement-concrete comprehensive performance to the dispersion effect of nano particle.
So having no in the research of modified by nano particles cement concrete in the pre-dispersed modified by nano particles TCS material mixing of water phase
The report of the inorganic salts aquation accelerators such as calcium chloride is added in the process.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is break through the bottleneck of the prior art, rational proportion nanoscale two
The inorganic salts aquation accelerator such as silicon oxide particle, calcium chloride and comb shape polycarboxylic acid dispersion/water-reducing agent, providing a kind of high intensity can
Injection-type bioactive materials and preparation method thereof are easy to reunite, cause when dispersing uneven to solve nanometer grade silica
The problems such as bioactive materials compression strength is lower, curing time is too long.
The technical problems to be solved by the invention are realized using following technical scheme.
A kind of high intensity injectable type bioactive materials, are made of the following components, including nanometer grade silica, silicic acid
Tricalcium powder and solidify liquid；
The mass ratio of the tricalcium silicate powder, nanometer grade silica and solidify liquid is 1:0.01-0.05:0.4-0.8.
Further, the solidify liquid is distilled water or deionized water containing calcium chloride and comb shape polycarboxylic acids；
The mass percent content that the calcium chloride accounts for solidify liquid is 1-25%, and the comb shape polycarboxylic acids accounts for the quality hundred of solidify liquid
Fractional content is 0.1-1%；
The comb shape polycarboxylic acids contains long side chain and short main chain.
Further, the nanosized silica particles partial size is 15-50 nm, the tricalcium silicate powder granule grain
Diameter is 0.1-100 μm, and the tricalcium silicate powder purity is 95% or more.
Further, the tricalcium silicate powder granule partial size is 0.1-10 μm.
A kind of preparation method of high intensity injectable type bioactive materials, specifically includes the following steps:
(1) preparation of tricalcium silicate powder
Tricalcium silicate presoma is prepared using wet chemistry method first, then obtains tricalcium silicate presoma through high-temperature calcination, ball milling
To tricalcium silicate powder；
(2) solidify liquid needed for weighing the tricalcium silicate powder and reaction in proportion, nanoscale dioxy is added into solidify liquid
Nanometer grade silica is uniformly dispersed by SiClx by ultrasonic vibration, finally that the tricalcium silicate powder and solidify liquid is abundant
It reconciles.
Further, step (1) the high-temperature calcination temperature is 1400-1450oC, calcination time are 6-12 h；It is described
Ball milling condition is planetary ball mill with 300-400 r/min ball milling 3-6 h.
Further, the mass ratio that feeds intake of the tricalcium silicate powder, nanometer grade silica and solidify liquid is 1:0.01-
0.05:0.4-0.8.
Further, the solidify liquid is distilled water or deionized water containing calcium chloride and comb shape polycarboxylic acids；
The mass percent content that the calcium chloride accounts for solidify liquid is 1-25%, and the comb shape polycarboxylic acids accounts for the quality hundred of solidify liquid
Fractional content is 0.1-1%；
The comb shape polycarboxylic acids contains long side chain and short main chain.
Further, the nanosized silica particles partial size is 15-50 nm, the tricalcium silicate powder granule grain
Diameter is 0.1-100 μm, and the tricalcium silicate powder purity is 95% or more,
Further, the tricalcium silicate powder granule partial size is 0.1-10 μm.
Further, the nanometer grade silica is the commercially available pure nanometer grade silica powder of analysis
Further, the TCS powder granule size may advantageously facilitate hydration reaction and reduce curing time.
Further, wet chemistry method preparation TCS is well-known technique.
Further, the comb shape polycarboxylic acids be containing long side chain, short main chain, comb shaped structure polycarboxylic acids.The carboxylic of birdsing of the same feather flock together
Acid is preferable to the dispersibility of dispersing nanoparticles in pure TCS powder.
Method for above-mentioned bioactive materials performance characterization is as follows:
A kind of compression strength and the measurement of curing time of high intensity injectable type bioactive materials: by the paste biology of modulation
Active material is prepared into the sample that diameter × highly is 6 × 12mm, and omnipotent test machine is utilized to carry out compressive strength determination；It presses
ISO6876:2001 proposed standard carries out curing time measurement to compound paste using penetrometer.
A kind of biological activity test of high intensity injectable type bioactive materials:
Biological activity test is carried out using in-vitro simulated body fluid immersion test to a kind of high-intensitive injectable type bioactive materials,
And X-ray diffraction (XRD) and scanning electron microscope (SEM) characterization are carried out to sample surfaces after immersion.
The beneficial effects of the present invention are:
The present invention will be the characteristics of the good self-curing performance of TCS powder, bioactivity and preferable mechanical property and nanoscale dioxy
SiClx accelerates TCS powder aquation, improve the microstructure of its hydrated product and calcium chloride substantially speeds up the solidification of TCS powder and comb
Shape polycarboxylic acids can be improved the effects of TCS powder fluidity and combine；Using having stronger space multistory steric effect and quiet
The comb shape polycarboxylic-acid dispersing agent of electric repulsion effect, rationally designs calcium chloride concentration in solidify liquid, passes through external ultrasound wave energy
Under assistance, the evenly dispersed of nanosized silica particles is not only realized, prevents nanosized silica particles to reunite existing
The generation of elephant, and calcium chloride is coated on nanosized silica particles surface on nanoscale, it optimizes
The synergistic effect of nanometer grade silica and calcium chloride and TCS powder comprehensive performance；Obtained bioactive materials can be fine
Be applied to human body bone and tooth defect fill, not only curing time is short and compression strength is higher for the material.
Detailed description of the invention
Fig. 1 is a kind of 1,3 and 7 day compression strength of high-intensitive injectable type bioactive materials in the embodiment of the present invention 1
With the change curve of nanometer grade silica additive amount；
Curing time and nanoscale dioxy of the Fig. 2 for high-intensitive injectable type bioactive materials a kind of in the embodiment of the present invention 2
The change curve of SiClx additive amount；
Fig. 3 be in the embodiment of the present invention 3 a kind of high-intensitive injectable type bioactive materials impregnate it is molten after in-vitro simulated body fluid
The change curve of liquid pH value and nanometer grade silica additive amount；
Fig. 4 impregnates 7 days tables for high-intensitive injectable type bioactive materials a kind of in the embodiment of the present invention 3 in simulated body fluid
Face XRD spectrum；
Fig. 5 impregnates 7 days for high-intensitive injectable type bioactive materials a kind of in the embodiment of the present invention 3 in simulated body fluid
SEM picture；
Fig. 6 is a kind of XRD spectrum of high-intensitive injectable type bioactive materials maintenance 7 days in the embodiment of the present invention 4.
Specific embodiment
Below with reference to the example content that the present invention is furture elucidated, but these examples are not limit the scope of the invention, all
The material of the technology and preparation realized based on above content of the present invention is all belonged to the scope of protection of the present invention.
Embodiment 1
(1) preparation of solidify liquid and TCS powder
It weighs pure 20 g of calcium chloride and 1 g of comb shape polycarboxylic acids of analysis and is dissolved in 79 g deionized waters and obtain special solidify liquid, disappear
Poison is enclosed in disinfection bottle, spare；
TCS presoma is prepared using wet chemistry method, accurately weighs 0.2 mol TEOS, 0.6 mol CaC2O4、0.8 mol
C2H5Deionized water and C is added in load weighted TEOS by the deionized water of OH, 90 ml or so2H5In the mixed solution of OH, use
Solution ph is adjusted to 1 by nitric acid, and stirring obtained evenly dispersed active SiO after 1 hour2Colloidal sol.By CaC2O4It is added to by several times
Active SiO under stirring2In colloidal sol, and obtained after setting 30 °C of stirrings 2 hours for the heating temperature of magnetic stirrer
SiO2And CaC2O4Mixed uniformly suspension slurry；Above-mentioned suspension slurry is placed 120oIt is sufficiently dry in C drying box, then through grinding
Mill obtains SiO2And CaC2O4Uniform mixed powder, and laminar raw material are pressed into 10 MPa pressure；By laminar TCS forerunner
Body is 1450oC is calcined 6 hours, and TCS after sintering is put into planetary ball mill to obtain TCS powder after 300 r/min ball milling 3 hours
Body, obtained TCS powder granule partial size are 0.1-100 μm, and purity is 95% or more；
(2) firstly, weighing TCS powder and solidify liquid by solid-to-liquid ratio 1:0.4, nanometer then is weighed by the 1-5% of TCS powder quality
Grade silicon dioxide, then nanometer grade silica is added in above-mentioned solidify liquid and is carried out ultrasonic disperse 30 minutes, nanoscale titanium dioxide
Silicon particle partial size is 15-50 nm；Finally TCS powder is added in solidify liquid and is sufficiently reconciled 1-2 minutes, mold is injected, 37
DEG C and 95% humidity under conserve 1 day after demould.Sample is put into deionized water again and is conserved, 7 days compression strength highests of the material
For 77 MPa, and there is excellent bioactivity.Wherein, the 1st, 3 and 7 day compression strength and nanometer grade silica additive amount
Change curve is as shown in Figure 1.
Embodiment 2
(1) preparation of solidify liquid and TCS powder
It weighs the pure 25 g calcium chloride of analysis and 1 g comb shape polycarboxylic acids is dissolved in 74 g distilled water and obtains special solidify liquid, sterilize,
It is enclosed in disinfection bottle, it is spare；
TCS presoma is prepared using wet chemistry method, then by TCS presoma through 1400o12 h of C high-temperature calcination, with 400 r/
6 h of min ball milling obtains TCS powder, and obtained TCS powder granule partial size is 0.1-100 μm, and purity is 95% or more；
(2) firstly, weighing TCS powder and solidify liquid by solid-to-liquid ratio 1:0.4, nanometer then is weighed by the 1-5% of TCS powder quality
Grade silicon dioxide, then nanometer grade silica is added in above-mentioned solidify liquid and is carried out ultrasonic disperse 30 minutes；Finally by TCS powder
It is added in solidify liquid and sufficiently reconciles 1-2 minutes, inject mold, conserved under 37 DEG C and 95% humidity, which can be in 30 minute
Solidification, and there is excellent bioactivity.Wherein, change curve such as Fig. 2 of curing time and nanometer grade silica additive amount
It is shown.
Embodiment 3
(1) preparation of solidify liquid and TCS powder
It weighs pure 1 g of calcium chloride and 0.5 g of comb shape polycarboxylic acids of analysis and is dissolved in 98.5 g deionized waters and obtain special solidify liquid,
Disinfection is enclosed in disinfection bottle, spare.
TCS presoma is prepared using wet chemistry method first, then by TCS presoma through 1430oC high-temperature calcination 8, with
4 h of 350r/min ball milling obtains TCS powder, and obtained TCS powder granule partial size is 0.1-10 μm, and purity is 95% or more；
(2) firstly, weighing TCS powder and solidify liquid by solid-to-liquid ratio 1:0.6, nanometer then is weighed by the 1-5% of TCS powder quality
Grade silicon dioxide, then nanometer grade silica is added in above-mentioned solidify liquid and is carried out ultrasonic disperse 30 minutes；Finally by TCS powder
It is added in solidify liquid and sufficiently reconciles 1-2 minutes, inject mold, conserved under 37 DEG C and 95% humidity, then impregnate simulated body fluid
In, which can induce hydroxyapatite to generate, and have excellent bioactivity.Wherein, which impregnates external mould
The change curve of solution ph and nanometer grade silica additive amount after quasi- body fluid in simulated body fluid as shown in figure 3, impregnate 7
It surface XRD spectrum and SEM picture is as shown in Figure 4, Figure 5.
Embodiment 4
(1) preparation of solidify liquid and TCS powder
It weighs the pure 20 g calcium chloride of analysis and 0.1 g comb shape polycarboxylic acids is dissolved in 79.9 g distilled water and obtains special solidify liquid,
Disinfection is enclosed in disinfection bottle, spare；
TCS presoma is prepared using wet chemistry method first, then by TCS presoma through 1420o9 h of C high-temperature calcination, with 380
5 h of r/min ball milling obtains TCS powder, and obtained TCS powder granule partial size is 0.1-10 μm, and purity is 95% or more；
(2) firstly, weighing TCS powder and solidify liquid by solid-to-liquid ratio 1:0.8, nanoscale then is weighed by the 1% of TCS powder quality
Silica, then nanometer grade silica is added in above-mentioned solidify liquid and is carried out ultrasonic disperse 30 minutes；Finally TCS powder is added
Enter sufficiently to reconcile in solidify liquid to can be obtained for 1-2 minutes and there is excellent life for the injectable type material for repairing tissue defect
Object activity.Wherein, the XRD spectrum of biomaterial maintenance 7 days is as shown in Figure 6.
Embodiment 5
(1) preparation of solidify liquid and TCS powder
It weighs the pure 20 g calcium chloride of analysis and 0.1 g comb shape polycarboxylic acids is dissolved in 79.9 g distilled water and obtains special solidify liquid,
Disinfection is enclosed in disinfection bottle, spare；
TCS presoma is prepared using wet chemistry method first, then by TCS presoma through 1450o6 h of C high-temperature calcination, with 300
3 h of r/min ball milling obtains TCS powder, and obtained TCS powder granule partial size is 0.1-10 μm, and purity is 95% or more；
(2) firstly, weighing TCS powder and solidify liquid by solid-to-liquid ratio 1:0.8, nanoscale then is weighed by the 5% of TCS powder quality
Silica, then nanometer grade silica is added in above-mentioned solidify liquid and is carried out ultrasonic disperse 30 minutes；Finally TCS powder is added
Enter sufficiently to reconcile in solidify liquid can be obtained within 1-2 minutes for repair tissue defect injectable type material.
A kind of compression strength and the measurement of curing time of high intensity injectable type bioactive materials: by the biology of modulation
Active material paste is prepared into the sample that diameter × highly is 6 × 12mm, and omnipotent test machine is utilized to carry out compressive strength determination；
By ISO6876:2001 proposed standard, curing time measurement is carried out to compound paste using penetrometer.
Fig. 1 is 1,3 and 7 day compression strength and nanoscale of a kind of high-intensitive injectable type bioactive materials embodiment 1
The relationship of silica additive amount.Fig. 1 the result shows that, when adding 3% nanometer grade silica, 1,3 and of complex cement slurry
7 days compression strength all reaches the peak under the conditions of, wherein 7 days compression strength reaches as high as 77 MPa.Fig. 2 is a kind of high intensity
The curing time of injectable type bioactive materials embodiment 2 and the relationship of nanometer grade silica additive amount.Fig. 2 result table
Bright, a kind of present invention curing time of high-intensitive injectable type bioactive materials above-mentioned can be according to nanoscale dioxy in system
The content of SiClx is adjusted, when adding 3% nanometer grade silica, minimum 30 points of the curing time of complex cement slurry
Clock.
A kind of biological activity test of high intensity injectable type bioactive materials:
Biological activity test is carried out using in-vitro simulated body fluid immersion test to a kind of high-intensitive injectable type bioactive materials,
And X-ray diffraction (XRD) and scanning electron microscope (SEM) characterization are carried out to sample surfaces after immersion.By to 3 He of embodiment
The material that embodiment 4 obtains is tested, available as shown in Figure 4 and Figure 6 as a result, showing a kind of high intensity of the invention
Injectable type bioactive materials surface can induce hydroxyapatite generation, show that a kind of high-intensitive injectable type of the invention is raw
Object active material has excellent bioactivity.
A kind of high-intensitive injectable type bioactive materials provided by the invention, existing excellent bioactivity, biofacies
Capacitive and preferable mechanical property, and it easily can be prepared into the cement material of paste or injectable as needed, satisfaction is faced
A variety of treatments that bed carries out the operation of bone tooth defect repair need, and are a kind of novel human body bone/tooth impairment renovation materials.
In conclusion the present invention propose using a kind of pre-dispersed nano silica of compatible comb shape polycarboxylic acids and calcium chloride without
Composite curing liquid, the high-purity tricalcium silicate of machine salt curing accelerator, the polycarboxylic acids give full play to space multistory steric effect, gram
Interference of the inorganic salts aquation accelerator to nano silica dispersibility is taken, promotes nano silica high in composite curing liquid
Effect dispersion can get 30-55 minutes ultrashort curing times, and 7 days compression strength is up to 61-77 MPa, and can induce hydroxyl phosphorus
The formation of lime stone.Compared with current material, material of the invention has excellent in mechanical performance, and rapid curing has superior bio
The characteristics such as activity.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes and improvements
It both falls in the scope of protection of present invention.The claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (10)
1. a kind of high intensity injectable type bioactive materials, which is characterized in that be made of the following components, including nanoscale dioxy
SiClx, tricalcium silicate powder and solidify liquid；
The mass ratio of the tricalcium silicate powder, nanometer grade silica and solidify liquid is 1:0.01-0.05:0.4-0.8.
2. a kind of high-intensitive injectable type bioactive materials according to claim 1, which is characterized in that the solidify liquid
For distilled water or deionized water containing calcium chloride and comb shape polycarboxylic acids；
The mass percent content that the calcium chloride accounts for solidify liquid is 1-25%, and the comb shape polycarboxylic acids accounts for the quality hundred of solidify liquid
Fractional content is 0.1-1%；
The comb shape polycarboxylic acids contains long side chain and short main chain.
3. a kind of high-intensitive injectable type bioactive materials according to claim 1 or 2, which is characterized in that described to receive
Meter level silica dioxide granule partial size is 15-50 nm, and the tricalcium silicate powder granule partial size is 0.1-100 μm, the silicic acid
Tricalcium powder purity is 95% or more.
4. a kind of high-intensitive injectable type bioactive materials according to claim 3, which is characterized in that the silicic acid three
Calcium powder body grain diameter is 0.1-10 μm.
5. a kind of preparation method of high intensity injectable type bioactive materials, which is characterized in that specifically includes the following steps:
(1) preparation of tricalcium silicate powder
Tricalcium silicate presoma is prepared using wet chemistry method first, then obtains tricalcium silicate presoma through high-temperature calcination, ball milling
To tricalcium silicate powder；
(2) solidify liquid needed for weighing the tricalcium silicate powder and reaction in proportion, nanoscale dioxy is added into solidify liquid
Nanometer grade silica is uniformly dispersed by SiClx by ultrasonic vibration, finally that the tricalcium silicate powder and solidify liquid is abundant
It reconciles.
6. a kind of preparation method of high-intensitive injectable type bioactive materials according to claim 5, which is characterized in that
Step (1) the high-temperature calcination temperature is 1400-1450oC, calcination time are 6-12 h；The ball milling condition is planetary ball mill
Machine is with 300-400 r/min ball milling 3-6 h.
7. a kind of preparation method of high-intensitive injectable type bioactive materials according to claim 5 or 6, feature exist
In the mass ratio that feeds intake of the tricalcium silicate powder, nanometer grade silica and solidify liquid is 1:0.01-0.05:0.4-0.8.
8. a kind of preparation method of high-intensitive injectable type bioactive materials according to claim 7, is characterized in that, institute
Stating solidify liquid is distilled water or deionized water containing calcium chloride and comb shape polycarboxylic acids；
The mass percent content that the calcium chloride accounts for solidify liquid is 1-25%, and the comb shape polycarboxylic acids accounts for the quality hundred of solidify liquid
Fractional content is 0.1-1%；
The comb shape polycarboxylic acids contains long side chain and short main chain.
9. a kind of preparation method of high-intensitive injectable type bioactive materials according to claim 8, is characterized in that, institute
Stating nanosized silica particles partial size is 15-50 nm, and the tricalcium silicate powder granule partial size is 0.1-100 μm, described
Tricalcium silicate powder purity is 95% or more.
10. a kind of preparation method of high-intensitive injectable type bioactive materials according to claim 9, feature exist
In the tricalcium silicate powder granule partial size is 0.1-10 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811256583.9A CN109432506A (en) | 2018-10-26 | 2018-10-26 | A kind of high intensity injectable type bioactive materials and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811256583.9A CN109432506A (en) | 2018-10-26 | 2018-10-26 | A kind of high intensity injectable type bioactive materials and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109432506A true CN109432506A (en) | 2019-03-08 |
Family
ID=65547781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811256583.9A Pending CN109432506A (en) | 2018-10-26 | 2018-10-26 | A kind of high intensity injectable type bioactive materials and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109432506A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112843341A (en) * | 2021-01-13 | 2021-05-28 | 安徽医科大学 | Injectable calcium silicate-based self-curing biological ceramic, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706504A (en) * | 2005-05-13 | 2005-12-14 | 中国科学院上海硅酸盐研究所 | Self-curing bioactive tricalcium silicate material and its prepn and use |
| CN101791427A (en) * | 2010-01-26 | 2010-08-04 | 南京工业大学 | Alkaline excitation nano silicon dioxide self-curing material with bioactivity and preparation method and application thereof |
| CN103833941A (en) * | 2014-03-03 | 2014-06-04 | 中科院广州化学有限公司 | Comb type polycarboxylic acid efficient ceramic water reducer and preparation method and application thereof |
| CN105999418A (en) * | 2016-06-20 | 2016-10-12 | 北京大学口腔医院 | Injectable bioactive bone cement material and preparation method thereof |
-
2018
- 2018-10-26 CN CN201811256583.9A patent/CN109432506A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706504A (en) * | 2005-05-13 | 2005-12-14 | 中国科学院上海硅酸盐研究所 | Self-curing bioactive tricalcium silicate material and its prepn and use |
| CN101791427A (en) * | 2010-01-26 | 2010-08-04 | 南京工业大学 | Alkaline excitation nano silicon dioxide self-curing material with bioactivity and preparation method and application thereof |
| CN103833941A (en) * | 2014-03-03 | 2014-06-04 | 中科院广州化学有限公司 | Comb type polycarboxylic acid efficient ceramic water reducer and preparation method and application thereof |
| CN105999418A (en) * | 2016-06-20 | 2016-10-12 | 北京大学口腔医院 | Injectable bioactive bone cement material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112843341A (en) * | 2021-01-13 | 2021-05-28 | 安徽医科大学 | Injectable calcium silicate-based self-curing biological ceramic, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7553362B2 (en) | High strength biological cement composition and using the same | |
| CN101157045B (en) | Complex self-curing material, method and application of bioactivity calcium phosphate/tricalcium silicate | |
| CN103819182B (en) | Calcium borate silicate biological material as well as preparation and application thereof | |
| CN1923302A (en) | Calcium sulfate semihydrate group combined self-curing bio-active material, preparation and application thereof | |
| Lin et al. | Preparation and characterization of novel alkali‐activated nano silica cements for biomedical application | |
| CN100406072C (en) | Bio-activity tricalcium silicate/semi water calcium sulphate composite self-solidification material, preparation and application | |
| TW200934461A (en) | Calcium silicate-based cements and manufacturing method thereof | |
| Li et al. | Facile synthesis and characterization of novel rapid-setting spherical sub-micron bioactive glasses cements and their biocompatibility in vitro | |
| CN109432506A (en) | A kind of high intensity injectable type bioactive materials and preparation method thereof | |
| Zhou et al. | Development of monetite–nanosilica bone cement: A preliminary study | |
| CN113209367B (en) | Active ion doped weak-crystallization carbonated hydroxyapatite particle artificial bone and preparation method and application thereof | |
| CN105079872B (en) | Artificial material for fine repairing and preparation method thereof | |
| CN101428152A (en) | Composite self-curing material of dicalcium silicate, preparation and uses thereof | |
| CN108653804A (en) | A kind of preparation method for mixing silicon calcium phosphate bone repair materials | |
| JP3718708B2 (en) | Calcium phosphate bioceramic sintered body and method for producing the same | |
| CN101791427B (en) | Alkaline excitation nano silicon dioxide self-curing material with bioactivity and preparation method and application thereof | |
| KR20210069759A (en) | nanobioactive glass cement comprising strontium doped bioactive glass nanoparticle and preparation method thereof | |
| CN105948012A (en) | Method for preparing beta-tricalcium phosphate crystal material under low temperature condition | |
| Wu et al. | Physico-chemical characterization, bioactivity evaluation and cytotoxicity of PDA nanoparticles doped tricalcium silicate cements | |
| CN104524638A (en) | Silicon oxide-calcium phosphate class composite nano-filler and preparation method thereof | |
| CN108424138A (en) | Siliceous modified grain boundary phase hydroxylapatite ceramic, bone injury repair material and preparation method thereof | |
| CN117062791A (en) | Hydraulic binders based on calcium silicate for forming composite materials with reinforcing properties | |
| CN101711892A (en) | Method for preparing nano-powder Si-HAC by ultrasonic copolymerization | |
| Li et al. | Fast-setting and high fracture toughness Ce-TZP/tricalcium silicate composite dental cement | |
| CN110201228A (en) | A kind of calcium phosphate bone cement and its preparation method and application containing decalcified bone matrix |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190308 |
|
| RJ01 | Rejection of invention patent application after publication |