CN104548195A - Mesoporous calcium magnesium silicate and polyetheretherketone composite, bone prosthesis as well as preparation method and application of composite - Google Patents
Mesoporous calcium magnesium silicate and polyetheretherketone composite, bone prosthesis as well as preparation method and application of composite Download PDFInfo
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- CN104548195A CN104548195A CN201410804632.3A CN201410804632A CN104548195A CN 104548195 A CN104548195 A CN 104548195A CN 201410804632 A CN201410804632 A CN 201410804632A CN 104548195 A CN104548195 A CN 104548195A
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Abstract
The invention discloses a mesoporous calcium magnesium silicate and polyetheretherketone composite, bone prosthesis as well as a preparation method and application of the composite. The preparation method of the mesoporous calcium magnesium silicate/polyetheretherketone composite comprises the following steps: uniformly mixing 20-40wt% of mesoporous calcium magnesium silicate and 6-80wt% of polyetheretherketone composite of 10-20microns so as to obtain mixed powder; mixing the mixed powder with absolute ethyl alcohol, ultrasonically dispersing, and evaporating the absolute ethyl alcohol at 58-62 DEG C so as to obtain composite powder; and pressing and molding the composite powder by virtue of a mould pressing method so as to obtain the composite. The mesoporous calcium magnesium silicate is uniform in particle size and is uniform in mesoporous pore size distribution. The composite is good in bioactivity and biocompatibility, relatively good in mechanical compatibility with bone tissue, and capable of stimulating bone growth, accelerating bone healing and shortening healing time of bone after implanting material. The bone prosthesis is good in bone mechanical compatibility and antibacterial property, high in strength, fatigue-resistant, good in corrosion resistance and long in service life.
Description
Technical field
The present invention relates to Material Field, particularly relate to mesoporous calcium magnesium silicate, Peek Composite Material and Preparation Method and application, also relate to a kind of bone repair and preparation method thereof.
Background technology
The bone implant material of current clinical practice is more titanio bone implant material and ceramic bone implant material, but those materials all still exist the shortcoming self being difficult to overcome.Metal structure character and bone differ greatly, and lack biological activity, cannot with bone formation Integrated implant, and easily cause bone resorption, and the stripping of metal ion easily causes the phenomenons such as hydrops, inflammation and necrosis; The shortcomings such as ceramic bone implant material then has not easily processing and forming, and toughness is poor.Therefore, the research and development of new substitute products are particularly important.
Polyether-ether-ketone (polyetheretherketone), is called for short PEEK, is to be developed in late 1970s by the ICI company of Britain and drop into the special engineered macromolecular material of suitability for industrialized production.Because it has excellent biocompatibility and antibiont respond, be with a wide range of applications at biomedical sector.
Polyether-ether-ketone (PEEK) not only has excellent biocompatibility and biological stability, and fatigue resistance is good, corrosion resistance is strong; The elastic modelling quantity of artificial bone manufactured with PEEK and osseous tissue match, and high strength, hard wear resistant and mechanical strength is not degenerated through sterilizing repeatedly.PEEK is designated as " best long-term bone grafting material ", and obtains FDA certification, and the U.S. develops the long-term osteoarthrosis, elbow joint etc. implanted with PEEK.Therefore, PEEK has more obvious advantage than metal and pottery, is applicable to long-term bone in body and implants.But PEEK lacks biological activity, can not with people's bone formation firmly key be combined.
There are some researches show, CaO-SiO
2the composite of-MgO system has good biological activity.Compared with β-TCP, akermanite (Ca
2mgSi
2o
7) lixiviating solution can better support bone marrow interstital stem cell (hBMSCs) breed and differentiation, akermanite has the skeletonization efficiency higher than β-TCP.Akermanite and bredigite (Ca
7mgSi
4o
16) one-component ceramic has good biodegradability, after soaking in SBF, surface energy generates apatite layer.In addition, akermanite and bredigite can discharge the different kinds of ions stimulating and promote osteoblastic propagation and differentiation under physiological environment.It should be noted that diopside (CaMgSi
2o
6) pottery, it has CaSiO
3mgSiO
3chemical composition, as in the research of biomaterial, do not show in experiment in vitro and have cytotoxicity to osteoblast, in research in vivo, this material can pass through Surface Creation calcium-phosphate layer, thus combines closely with bone.But, CaO-SiO
2the shortcomings such as-MgO base bioceramic fragility is large, and mechanical property is not high, and elastic modelling quantity is not enough, limit its application.
Summary of the invention
Technical problem to be solved by this invention is to overcome that the mechanical compatibility of existing bone renovating material is not good and bone renovating material that is that cause stress shielding to cause loosens and bone resorption, or knitting speed is excessively slow, lack biological activity, cannot with the defect of bone formation secure bond.The invention provides a kind of mesoporous calcium magnesium silicate and preparation method thereof, a kind of mesoporous calcium magnesium silicate/Peek Composite Material and Preparation Method and application, and a kind of bone repair obtained by this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material and preparation method thereof.The uniform particle sizes of this mesoporous calcium magnesium silicate, and mesoporous pore size is evenly distributed.This mesoporous calcium magnesium silicate/polyether-ether-ketone composite material has good biological activity and biocompatibility, has good mechanical compatibility with osseous tissue, can stimulation of bone growth, and accelerated bone heals, and reduces the healing time after bone implant material.This mesoporous calcium magnesium silicate/polyether-ether-ketone composite material simple for process, can prepare the bone repair of difformity, specification and mechanical property according to the preparation technology of this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material of the corresponding adjustment of clinical demand.This bone repair has good biocompatibility, biological activity, the biomechanics of bone compatibility and antibiotic property, can shorten bone healing time, and its intensity is high, endurance, corrosion resistance are good, long service life.Can not be caused inflammation after the implantation of this bone repair reaction, and the mechanical properties such as its elastic modelling quantity, toughness and fracture strength are mated with people's bone photo, the bone renovating material that stress shielding can not be caused to cause loosens and the negative effect such as bone resorption, can meet the clinical needs for Bone Defect Repari.
The present invention solves the problems of the technologies described above by the following technical programs.
The invention provides a kind of preparation method of mesoporous calcium magnesium silicate, it comprises the steps:
(1) P123, water and dehydrated alcohol are mixed, to solution clarification, at 36 DEG C ~ 40 DEG C, add hydrochloric acid be uniformly mixed, then TEOS is dropped in solution, be stirred to after white opacity appears in solution, add four water-calcium nitrate and magnesium nitrate hexahydrate, continue stirring 1 ~ 2 hour, obtain reactant liquor; Wherein, the mass ratio of P123, water and dehydrated alcohol is 1: (36 ~ 36.5): 1, the mass volume ratio of P123 and hydrochloric acid is 1g: (2.8 ~ 3) mL, the mass ratio of P123 and TEOS is 1: (2 ~ 2.3), and the mass ratio of P123, four water-calcium nitrate and magnesium nitrate hexahydrate is 1: (1.1 ~ 1.3): (1.2 ~ 1.4);
(2) by reactant liquor ageing 3 ~ 4 days at 92 DEG C ~ 98 DEG C, then sucking filtration removing upper liquid, carries out drying by precipitate at 78 DEG C ~ 82 DEG C, then sinters 5 ~ 7 hours at 540 DEG C ~ 560 DEG C, to obtain final product.
In step (1), described P123 is polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (EO well known in the art
20pO
70eO
20).
In step (1), described water is the water that this area routine uses, and is generally deionized water.
In step (1), described in add hydrochloric acid temperature be preferably 38 DEG C.
In step (1), described hydrochloric acid is the hydrochloric acid that this area routine uses, and the concentration of described hydrochloric acid is preferably 11.9mol/L.
In step (1), described TEOS is the ethyl orthosilicate that this area routine uses.The speed of described dropping is preferably 8/min ~ 20 droplet/min.
In step (2), the method for described ageing and condition are method and the condition of this area routine.The temperature of described ageing is preferably 95 DEG C.The time of described ageing is preferably 3 days.Described ageing is generally carried out in baking oven.
In step (2), the method for described drying and condition are method and the condition of this area routine.The temperature of described drying is preferably 80 DEG C.
In step (2), the method for described sintering and condition are method and the condition of this area routine.The temperature of described sintering is preferably 550 DEG C, and the time of described sintering is preferably 6 hours.
In a better embodiment of the present invention, the preparation method of described mesoporous calcium magnesium silicate, it comprises the steps:
(1) dehydrated alcohol of the water of P123,217g of 6.0g and 6g is mixed, to solution clarification, at 38 DEG C, add 17mL concentration is that the hydrochloric acid of 11.9mol/L is uniformly mixed, then the TEOS of 12.9g is dropped in solution, be stirred to after white opacity appears in solution, add the four water-calcium nitrate of 7.3g and the magnesium nitrate hexahydrate of 7.9g, continue stirring 1 hour, obtain reactant liquor;
(2) by reactant liquor ageing 3 days at 95 DEG C, then sucking filtration removing upper liquid, carries out drying by precipitate at 80 DEG C, then sinters 6 hours at 550 DEG C, to obtain final product.
The mesoporous pore size of the mesoporous calcium magnesium silicate obtained by preparation method of the present invention is 2nm ~ 5nm, and particle diameter is 0.2 μm ~ 1 μm.
Present invention also offers a kind of mesoporous calcium magnesium silicate obtained by above-mentioned preparation method, the mesoporous pore size of described mesoporous calcium magnesium silicate is 2nm ~ 5nm, and the particle diameter of described mesoporous calcium magnesium silicate is 0.2 μm ~ 1 μm.
Present invention also offers a kind of preparation method of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material, it comprises the steps:, by raw material Homogeneous phase mixing, to obtain mixed-powder, and described raw material is described mesoporous calcium magnesium silicate and polyether-ether-ketone; Then by described mixed-powder and dehydrated alcohol mixing, ultrasonic disperse, then evaporates dehydrated alcohol, obtains composite powder at 58 DEG C ~ 62 DEG C; Adopt die pressing by described composite powder machine-shaping, to obtain final product; Wherein, the consumption of described mesoporous calcium magnesium silicate accounts for the 20wt% ~ 40wt% of raw material gross weight, and the consumption of described polyether-ether-ketone accounts for the 60wt% ~ 80wt% of raw material gross weight; The particle diameter of described polyether-ether-ketone is 10 μm ~ 20 μm.
Wherein, the particle diameter of described polyether-ether-ketone powder is preferably 10 μm ~ 15 μm.
Wherein, the method for described mixing and condition can be method and the condition of this area routine, are as the criterion with mix homogeneously.Described mixing is preferably carried out in mixer.
Wherein, the consumption of described dehydrated alcohol is conventional amount used, fully disperses to be as the criterion to make described mixed-powder.The temperature of described evaporation dehydrated alcohol is preferably 60 DEG C.The time of described ultrasonic disperse is preferably 15min ~ 30min.The power of described ultrasonic disperse is preferably 60W ~ 90W.
Wherein, the method for described die pressing and condition can be method and the condition of this area routine.Described die pressing is preferably undertaken by following operational approach: by compressing for described mixed-powder, then heat up, sinter molding; The speed of described intensification is 1 DEG C/min ~ 4 DEG C/min; The temperature of described sintering is 350 DEG C ~ 360 DEG C; The temperature retention time of described sintering is 2 hours ~ 3 hours, is preferably 2 hours.
In the present invention, the shape of the mesoporous calcium magnesium silicate/polyether-ether-ketone composite material obtained after described machine-shaping is not limit.If mould used in described machine-shaping is the mould of bone repair product, then described mesoporous calcium magnesium silicate/polyether-ether-ketone composite material directly can be used as bone repair.If mould used in described machine-shaping is not the mould of bone repair product, then by the operation of follow-up processed, the operations such as such as grinding, machining, to prepare the bone repair of required form.
Present invention also offers a kind of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material obtained by above-mentioned preparation method.
In the present invention, described mesoporous calcium magnesium silicate/polyether-ether-ketone composite material is a kind of composite by mesoporous calcium magnesium silicate reinforced polyether ether ketone.
Present invention also offers the application of described mesoporous calcium magnesium silicate/polyether-ether-ketone composite material in bone repair.
Wherein, described bone repair is spinal bone dummy or tooth implant.Described spinal bone dummy, also referred to as Invasive lumbar fusion device, comprises strength Invasive lumbar fusion device and breast/waist Invasive lumbar fusion device.
Present invention also offers a kind of preparation method of bone repair, it comprises the steps:, by raw material Homogeneous phase mixing, to obtain mixed-powder, and described raw material is described mesoporous calcium magnesium silicate and polyether-ether-ketone; Then described mixed-powder is mixed with dehydrated alcohol, ultrasonic disperse, then at 58 DEG C ~ 62 DEG C, evaporate dehydrated alcohol, obtain composite powder; Described composite powder is carried out molding sintering molding in the mould of bone repair product, to obtain final product; Wherein, the consumption of described mesoporous calcium magnesium silicate accounts for the 20wt% ~ 40wt% of raw material gross weight, and the consumption of described polyether-ether-ketone accounts for the 60wt% ~ 80wt% of raw material gross weight; The particle diameter of described polyether-ether-ketone is 10 μm ~ 20 μm.
Wherein, the particle diameter of described polyether-ether-ketone powder is preferably 10 μm ~ 15 μm.
Wherein, the method for described mixing and condition can be method and the condition of this area routine, are as the criterion with mix homogeneously.Described mixing is preferably carried out in mixer.
Wherein, the consumption of described dehydrated alcohol is conventional amount used, fully disperses to be as the criterion to make described mixed-powder.The temperature of described evaporation dehydrated alcohol is preferably 60 DEG C.The time of described ultrasonic disperse is preferably 15min ~ 30min.The power of described ultrasonic disperse is preferably 60W ~ 90W.
Wherein, the mould of described bone repair product is the conventional mould used when preparing bone repair product, is preferably the mould of spinal bone dummy or the mould of tooth implant.Described spinal bone dummy, also referred to as Invasive lumbar fusion device, comprises strength Invasive lumbar fusion device and breast/waist Invasive lumbar fusion device.
Wherein, the method for described molding sintering molding and condition can be method and the condition of this area routine.Described molding sintering molding is preferably undertaken by following operational approach: by compressing for described mixed-powder, then heat up, sinter molding; The speed of described intensification is 1 DEG C/min; The temperature of described sintering is 350 DEG C ~ 360 DEG C; The temperature retention time of described sintering is 2 hours ~ 3 hours, is preferably 2 hours.
In the present invention, in the preparation method of described bone repair, after described machine-shaping, preferably also carry out surface coarsening process.Described surface coarsening process is preferably carried out in the steps below: use surface coarsening machine, with mesoporous calcium silicates magnesium granules, surface coarsening is carried out to the block that described machine-shaping obtains, form to described block surface the porous surface that aperture is 100 μm ~ 200 μm.The particle diameter of described mesoporous calcium magnesium silicate is preferably 100 μm ~ 500 μm.
Present invention also offers a kind of bone repair obtained by above-mentioned preparation method.
Wherein, described bone repair is spinal bone dummy or tooth implant.Described spinal bone dummy, also referred to as Invasive lumbar fusion device, comprises strength Invasive lumbar fusion device and breast/waist Invasive lumbar fusion device.
In the present invention, the shape of described bone repair can according to actual needs by selecting different moulds to change with specification.
In the present invention, the mechanical performance index of described Bone Defect Repari is roughly as follows:
Elastic modelling quantity is 4GPa ~ 6GPa, and comprcssive strength is 117MPa ~ 160GPa, and tensile strength is 76MPa ~ 105MPa, and bending strength is 86MPa ~ 115MPa.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can combination in any, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is:
(1) particle diameter of mesoporous calcium magnesium silicate of the present invention is 0.2 μm ~ 1 μm, and its even particle size distribution, its mesoporous pore size is 2nm ~ 5nm, and mesoporous pore size is evenly distributed.
(2) mesoporous calcium magnesium silicate/polyether-ether-ketone composite material of the present invention is simple for process, can prepare the bone repair of difformity, specification and mechanical property according to the preparation technology of this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material of the corresponding adjustment of clinical demand.
(3) adopt surface texture technology to process composite material molded body surface, form loose structure at composite material surface, osteocyte/osseous tissue is easily grown in porous hole, uses osseous tissue to be formed with implant and is firmly combined.
(4) mesoporous calcium magnesium silicate/polyether-ether-ketone composite material of the present invention has good biological activity and biocompatibility, has good mechanical compatibility with osseous tissue, can stimulation of bone growth, and accelerated bone heals, and reduces the healing time after bone implant material.
(5) bone repair of the present invention has good biocompatibility, biological activity, the biomechanics of bone compatibility, can shorten bone healing time.Can not be caused inflammation after using this bone repair to implant reaction, and the mechanical properties such as its elastic modelling quantity, toughness and fracture strength are mated with people's bone photo, the bone renovating material that stress shielding can not be caused to cause loosens and the negative effect such as bone resorption, can meet the clinical needs for Bone Defect Repari.
Accompanying drawing explanation
Fig. 1 is stereoscan photograph and the transmission electron microscope photo of mesoporous calcium magnesium silicate in embodiment 1.
Fig. 2 is the shape picture of the mesoporous calcium magnesium silicate/polyether-ether-ketone composite material sample (Φ 10 × 2mm) used in the cytotoxicity test experiments of effect example 2.
Fig. 3 is the mesoporous calcium magnesium silicate/polyether-ether-ketone composite material optical density figure carrying out cytotoxicity experiment in effect example 2.
Fig. 4 is the relative rate of increase of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material that records of the cell adhesion proliferation experiment of effect example 3 and the comparison diagram of the relative rate of increase of polyetheretherketonematerials materials.
Fig. 5 is the cell adhesion propagation stereoscan photograph of effect example 3.
Fig. 6 is the sample photo of the bone repair in effect example 4.
Fig. 7 is the stereoscan photograph of the bone repair in effect example 4.
Fig. 8 is the gross examination of skeletal muscle photo in effect example 4 after dog femoral defect place implantable bone repairs March.
Fig. 9 is that the bone repair in effect example 4 implants the tissue slice of dog femoral defect place after 3 months.
Figure 10 is the gross examination of skeletal muscle photo in effect example 4 after Canis familiaris L. Alveolar Bone Defect place implantable bone repairs March.
Figure 11 is that the bone repair in effect example 4 implants the tissue slice of Canis familiaris L. Alveolar Bone Defect place after 3 months.
Detailed description of the invention
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
In following embodiment, the relative molecular mass of P123 used is 5800, is purchased from Aldrich company.
Embodiment 1
A preparation method for mesoporous calcium magnesium silicate, it comprises the steps:
(1) dehydrated alcohol of the water of P123,217g of 6.0g and 6g is mixed, to solution clarification, at 38 DEG C, add 17mL concentration is that the hydrochloric acid of 11.9mol/L is uniformly mixed, then the TEOS of 12.9g is dropped in solution with the speed of 8/min ~ 20 droplet/min, be stirred to after white opacity appears in solution, add the four water-calcium nitrate of 7.3g and the magnesium nitrate hexahydrate of 7.9g, continue stirring 1 hour, obtain reactant liquor;
(2) by reactant liquor ageing 3 days at 95 DEG C, then sucking filtration removing upper liquid, carries out drying by precipitate at 80 DEG C, then sinters 6 hours at 550 DEG C, to obtain final product.
The stereoscan photograph of this mesoporous calcium magnesium silicate and transmission electron microscope photo are shown in Fig. 1 (a), (b) and Fig. 1 (c), (d) respectively; The mesoporous pore size of this mesoporous calcium magnesium silicate is at 2nm ~ 5nm, and particle diameter is 0.2 ~ 1 μm, its even particle size distribution.
Embodiment 2
The preparation method of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material, it comprises the steps:
By mesoporous silicic acid calcium-magnesium powder end obtained for 2kg (20wt%) embodiment 1 and 8kg (80wt%) polyether-ether-ketone powder (particle diameter is 10 μm) Homogeneous phase mixing in mixer, obtain mixed-powder; Mixed-powder is mixed with dehydrated alcohol, with the power ultrasonic of 60W dispersion 15min, is then placed in evaporation dehydrated alcohol in 60 DEG C of baking ovens, obtains composite powder; Then with mould by compressing for composite powder (using the mould of non-bone repair product), then heat up in sintering furnace, sinter molding, to obtain final product; Wherein, sintering temperature is 355 DEG C; The programming rate of sintering furnace is 1 DEG C/min; Temperature retention time is 2 hours.The mechanical property of this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material is in table 1.
Embodiment 3
The preparation method of bone repair, it comprises the steps:
Raw material Homogeneous phase mixing is carried out in mesoporous silicic acid calcium-magnesium powder end obtained for 4kg (40wt%) embodiment 1 and 5kg (50wt%) polyether-ether-ketone powder (particle diameter is 10 μm) in mixer, obtains mixed-powder; Mixed-powder is mixed with dehydrated alcohol, with the power ultrasonic of 90W dispersion 30min, is then placed in evaporation dehydrated alcohol in 58 DEG C of baking ovens, obtains composite powder; Then with mould by compressing for composite powder (using the mould of non-bone repair product), then heat up in sintering furnace, sinter molding, to obtain final product; Wherein, sintering temperature is 360 DEG C; The programming rate of sintering furnace is 2 DEG C/min; Temperature retention time is 2.5 hours.The mechanical property of this bone repair is in table 1.
Embodiment 4
The preparation method of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material, it comprises the steps:
Raw material Homogeneous phase mixing is carried out in mesoporous silicic acid calcium-magnesium powder end obtained for 2kg (20wt%) embodiment 1 and 8kg (80wt%) polyether-ether-ketone powder (particle diameter is 10 μm) in mixer, obtains mixed-powder; Mixed-powder is mixed with dehydrated alcohol, with the power ultrasonic of 60W dispersion 30min, is then placed in evaporation dehydrated alcohol in 62 DEG C of baking ovens, obtains composite powder; Then with mould by compressing for composite powder (using the mould of non-bone repair product), then heat up in sintering furnace, sinter molding, to obtain final product; Wherein, sintering temperature is 350 DEG C; The programming rate of sintering furnace is 1 DEG C/min; Temperature retention time is 2 hours.The mechanical property of this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material is in table 1.
Embodiment 5
The preparation method of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material, it comprises the steps:
Raw material Homogeneous phase mixing is carried out in mesoporous silicic acid calcium-magnesium powder end obtained for 3kg (30wt%) embodiment 1 and 7kg (70wt%) polyether-ether-ketone powder (particle diameter is 10 μm) in mixer, obtains mixed-powder; Mixed-powder is mixed with dehydrated alcohol, with the power ultrasonic of 90W dispersion 15min, is then placed in evaporation dehydrated alcohol in 62 DEG C of baking ovens, obtains composite powder; Then with mould by compressing for composite powder (using the mould of non-bone repair product), then heat up in sintering furnace, sinter molding, to obtain final product; Wherein, sintering temperature is 360 DEG C; The programming rate of sintering furnace is 4 DEG C/min; Temperature retention time is 3 hours.The mechanical property of this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material is in table 1.
Embodiment 6
The preparation method of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material, it comprises the steps:
Raw material Homogeneous phase mixing is carried out in mesoporous silicic acid calcium-magnesium powder end obtained for 4kg (40wt%) embodiment 1 and 6kg (60wt%) polyether-ether-ketone powder (particle diameter is 10 μm) in mixer, obtains mixed-powder; Mixed-powder is mixed with dehydrated alcohol, with the power ultrasonic of 90W dispersion 30min, is then placed in evaporation dehydrated alcohol in 60 DEG C of baking ovens, obtains composite powder; Then with mould by compressing for composite powder (using the mould of non-bone repair product), then heat up in sintering furnace, sinter molding, to obtain final product; Wherein, sintering temperature is 355 DEG C; The programming rate of sintering furnace is 2 DEG C/min; Temperature retention time is 2 hours.The mechanical property of this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material is in table 1.
Embodiment 7
The preparation method of bone repair, it comprises the steps:
Operate according to the composition of raw materials of embodiment 2 and preparation method, in the mould of dog femoral dummy after injection mo(u)lding, carry out the operation of surface coarsening process, specific as follows: to use surface coarsening machine, with mesoporous calcium silicates magnesium granules, surface coarsening process is carried out to the block after molding, form to described block surface the porous surface that aperture is 100 μm ~ 200 μm, obtain bone repair; Wherein, the particle diameter of mesoporous calcium magnesium silicate aggregate particle is 200 μm ~ 300 μm.
Embodiment 8
The preparation method of bone repair, it comprises the steps:
Operate according to the composition of raw materials of embodiment 5 and preparation method, carry out molding sintering molding in the mould of ridge Invasive lumbar fusion device product after, carry out the operation of surface coarsening process, specific as follows: to use surface coarsening machine, with mesoporous calcium silicates magnesium granules, surface coarsening process is carried out to the block after molding, form to described block surface the porous surface that aperture is 100 μm ~ 200 μm, obtain bone repair; Wherein, the particle diameter of mesoporous calcium magnesium silicate aggregate particle is 100 μm ~ 300 μm.Fig. 6 is shown in by the photo of this bone repair.After carrying out surface coarsening process, Fig. 7 is shown in by scanning electron microscope (SEM) photo of this bone repair.
Embodiment 9
The preparation method of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material, it comprises the steps:
By mesoporous silicic acid calcium-magnesium powder end obtained for 2kg (20wt%) embodiment 1 and 8kg (80wt%) polyether-ether-ketone powder (particle diameter is 20 μm) Homogeneous phase mixing in mixer, obtain mixed-powder; Mixed-powder is mixed with dehydrated alcohol, with the power ultrasonic of 60W dispersion 30min, is then placed in evaporation dehydrated alcohol in 58 DEG C of baking ovens, obtains composite powder; Then with mould by compressing for composite powder (using the mould of non-bone repair product), then heat up in sintering furnace, sinter molding, to obtain final product; Wherein, sintering temperature is 355 DEG C; The programming rate of sintering furnace is 2 DEG C/min; Temperature retention time is 2 hours.The mechanical property of this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material is in table 1.
Embodiment 10
The preparation method of mesoporous calcium magnesium silicate polyether-ether-ketone composite material, it comprises the steps:
Raw material Homogeneous phase mixing is carried out in mesoporous silicic acid calcium-magnesium powder end obtained for 2kg (20wt%) embodiment 1 and 8kg (80wt%) polyether-ether-ketone powder (particle diameter is 15 μm) in mixer, obtains mixed-powder; Mixed-powder is mixed with dehydrated alcohol, with the power ultrasonic of 90W dispersion 15min, is then placed in evaporation dehydrated alcohol in 60 DEG C of baking ovens, obtains composite powder; Then with mould by compressing for composite powder (using the mould of non-bone repair product), then heat up in sintering furnace, sinter molding, to obtain final product; Wherein, sintering temperature is 355 DEG C; The programming rate of sintering furnace is 2 DEG C/min; Temperature retention time is 2 hours.The mechanical property of this mesoporous calcium magnesium silicate/polyether-ether-ketone composite material is in table 1.
Comparative example 1
Raw material: the mesoporous silicic acid calcium-magnesium powder end that 1kg embodiment 1 is obtained and 9kg polyether-ether-ketone powder (particle diameter is 10 μm), carries out the preparation of composite according to the preparation method of embodiment 2.The mechanical property of this composite is in table 1.
Comparative example 2
Raw material: 2kg mesoporous silicic acid calcium-magnesium powder end (particle diameter is 10 μm) and 8kg polyether-ether-ketone powder (particle diameter is 10 μm), carry out the preparation of composite according to the preparation method of embodiment 2.The mechanical property of this composite is in table 1.
Comparative example 3
Raw material: the mesoporous silicic acid calcium-magnesium powder end that 5kg embodiment 1 is obtained and 5kg polyether-ether-ketone powder (particle diameter is 10 μm), carries out the preparation of composite according to the preparation method of embodiment 2.The mechanical property of this composite is in table 1.
Effect example 1
Mechanical property test:
Carried out Mechanics Performance Testing to the bone repair of embodiment 2 ~ 10 and comparative example 1 ~ 3, test result is in table 1.
The mechanical property of the bone repair of each embodiment of table 1 and comparative example
From table 1, compared to the composite obtained by comparative example, the elastic modelling quantity of the mesoporous calcium magnesium silicate/polyether-ether-ketone composite material of the present invention and people's bone closer to, and parameters index in mechanical property is more excellent, is very suitable for the substitution material (bone and tooth) as human body hard tissue.
Effect example 2
The cytotoxicity experiment of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material:
Mesoporous calcium magnesium silicate/the polyether-ether-ketone composite material obtained to embodiment 2 and 5 carries out cytotoxicity experiment, and wherein sample diameter is 10mm, and thickness is 2mm, specifically sees Fig. 2.The concrete grammar of cytotoxicity experiment is as follows:
According to the biological safety of ISO:10993-5 cytotoxicity standard testing composite.At 37 DEG C, two kinds of samples (200mg/mL) in serum-free cell culture medium soak 24 hours, filter to obtain lixiviating solution.With the concentration in 3 × 102/ holes, fibroblast is inoculated into 96 hole tissue culturing plates, after continuing to hatch 1 day, discard culture medium, PBS cleans 3 times; Add the lixiviating solution containing 10%FBS, continue cultivation 1 day; Do not add material lixiviating solution containing 10%FBS as experiment blank group.When testing time point, every hole adds 30 pi of MTT solution, continues to hatch cultivation after 4 hours, discards culture fluid, PBS cleans 3 times, and every hole adds 100 microlitre DMSO, and room temperature left standstill after 10 minutes, by microplate reader at 490nm wavelength place, survey the absorbance of solution, see Fig. 3.As seen from Figure 3, compared with blank (tissue culturing plate TCP), the absorbance of experimental group (sample of embodiment 1 and 4) does not have significant difference, shows that these two kinds of composites do not have negative effect to fibroblastic growth.Known as calculated, the ratio of the cell survival rate of the cell in material lixiviating solution and blank group, all more than 95%, proves that these two samples all do not have toxicity to fibroblast.
Effect example 3
Cell adhesion proliferation experiment
Mesoporous calcium magnesium silicate/the polyether-ether-ketone composite material obtained to embodiment 2 and 5 carries out cell adhesion proliferation experiment, and wherein sample diameter is 10mm, and thickness is 2mm, specifically sees Fig. 2.The concrete grammar of cell adhesion proliferation experiment is as follows:
(1) mtt assay is adopted to carry out cell proliferation experiment, by two kinds of samples (often kind of three groups of Duplicate Samples, polyetheretherketonematerials materials) use the cultivation carrying out MC3T3-E1 containing 10% hyclone culture fluid, inoculate with every hole 1W cell, respectively at 1, 3, 5 days, every hole adds MTT solution 40 μ L, continue to cultivate 4h, stop cultivating, culture supernatant in careful absorption hole, every hole adds 150 μ L DMSO, decolorization swinging table concussion 10min, 490nm (570nm) wavelength is selected after crystal is fully dissolved, enzyme-linked immunosorbent assay instrument measures each hole absorbance value, obtain result, result is as Fig. 4.
(2) MC3T3-E1 cell is seeded in two kinds of samples (three groups of Duplicate Samples with every hole 1w quantity, polyetheretherketonematerials materials) cultivate, after using fixative that cell is fixing respectively at 12h, 24h, under scanning electron microscope, observation of cell adheres to situation, as Fig. 5.In Fig. 5, (1) and (3) is cell adhesion situation in polyether-ether-ketone group, (2), (4) are mesoporous calcium magnesium silicate/polyether-ether-ketone composite material group cell adhesion situation, result shows, all there are cell adhesion and propagation in bi-material surface, but the cell quantity that mesoporous calcium magnesium silicate/polyether-ether-ketone composite material group adheres to is more and have and better adhere to form, show that it has better biological activity and cell compatibility.
Effect example 4
Animal implants experiment:
(1) bone repair (concrete shape is shown in Fig. 6, and stereoscan photograph is shown in Fig. 7) of made for embodiment 8 dog femoral is implanted dog femoral defect place.Fig. 8 is the implantation gross examination of skeletal muscle photo that after 3 months, digital camera is taken the photograph, and arrow indication is implantable bone dummy.This bone repair is implanted the tissue slice of dog femoral defect place after 3 months by Fig. 9.In Fig. 9, B represents bone parts, and M represents material component, and arrow indication is the bound fraction of material and bone.Fig. 9 is visible, and made bone repair is directly combined with bone, and junction is without connective tissue (Integrated implant), therefore this dummy has good biocompatibility and biological activity, can be used as body implanting material, repairs or alternative tissue.Result shows, this bone repair can impel surrounding bone tissue growth, and organizes with its surrounding bone and directly form strong bonded.
(2) made for embodiment 8 bone repair (outward appearance is shown in Fig. 6) is implanted Labrador Retriever Alveolar Bone Defect place, take out after raising March, Figure 10 is shown in by outward appearance photo, and arrow indication is former defect position.Picture is visible, and material is combined with tissue tight of dog defect place, and does not occur inflammation and other untoward reaction, completes Alveolar Bone Defect reparation.It being made section gained picture is Figure 11, and wherein the representative part of B is osseous tissue part, and M represents material component, and arrow indication is both boundary lines, and by Tu Ke get, junction is without connective tissue, and material and osseous tissue directly combine closely (Integrated implant).Illustrate thus, dummy promotes its surrounding bone tissue growth, and bone repair and osseous tissue are stablized and combine closely, and connect as a whole, complete the alternative reparation of Cranial defect.
Claims (10)
1. a preparation method for mesoporous calcium magnesium silicate, is characterized in that, it comprises the steps:
(1) P123, water and dehydrated alcohol are mixed, to solution clarification, at 36 DEG C ~ 40 DEG C, add hydrochloric acid be uniformly mixed, then TEOS is dropped in solution, be stirred to after white opacity appears in solution, add four water-calcium nitrate and magnesium nitrate hexahydrate, continue stirring 1 ~ 2 hour, obtain reactant liquor; Wherein, the mass ratio of P123, water and dehydrated alcohol is 1: (36 ~ 36.5): 1, the mass volume ratio of P123 and hydrochloric acid is 1g: (2.8 ~ 3) mL, the mass ratio of P123 and TEOS is 1: (2 ~ 2.3), and the mass ratio of P123, four water-calcium nitrate and magnesium nitrate hexahydrate is 1: (1.1 ~ 1.3): (1.2 ~ 1.4);
(2) by reactant liquor ageing 3 ~ 4 days at 92 DEG C ~ 98 DEG C, then sucking filtration removing upper liquid, carries out drying by precipitate at 78 DEG C ~ 82 DEG C, then sinters 5 ~ 7 hours at 540 DEG C ~ 560 DEG C, to obtain final product.
2. preparation method as claimed in claim 1, is characterized in that, in step (1), described in add hydrochloric acid temperature be 38 DEG C; And/or in step (1), the concentration of described hydrochloric acid is 11.9mol/L; And/or in step (1), the speed of described dropping is 8/min ~ 20 droplet/min; And/or in step (2), the temperature of described ageing is 95 DEG C, and the time of described ageing is 3 days; And/or in step (2), the temperature of described drying is 80 DEG C; And/or in step (2), the temperature of described sintering is 550 DEG C, and the time of described sintering is 6 hours.
3., by the mesoporous calcium magnesium silicate that preparation method described in claim 1 or 2 is obtained, it is characterized in that, the mesoporous pore size of described mesoporous calcium magnesium silicate is 2nm ~ 5nm, and the particle diameter of described mesoporous calcium magnesium silicate is 0.2 μm ~ 1 μm.
4. a preparation method for mesoporous calcium magnesium silicate/polyether-ether-ketone composite material, is characterized in that, it comprises the steps:, by raw material Homogeneous phase mixing, to obtain mixed-powder, and described raw material is mesoporous calcium magnesium silicate as claimed in claim 3 and polyether-ether-ketone; Then by described mixed-powder and dehydrated alcohol mixing, ultrasonic disperse, then evaporates dehydrated alcohol, obtains composite powder at 58 DEG C ~ 62 DEG C; Adopt die pressing by described composite powder machine-shaping, to obtain final product; Wherein, the consumption of described mesoporous calcium magnesium silicate accounts for the 20wt% ~ 40wt% of raw material gross weight, and the consumption of described polyether-ether-ketone accounts for the 60wt% ~ 80wt% of raw material gross weight; The particle diameter of described polyether-ether-ketone is 10 μm ~ 20 μm.
5. preparation method as claimed in claim 4, it is characterized in that, the particle diameter of described polyether-ether-ketone powder is 10 μm ~ 15 μm; And/or the temperature of described evaporation dehydrated alcohol is 60 DEG C; And/or the time of described ultrasonic disperse is 15min ~ 30min, the power of described ultrasonic disperse is 60W ~ 90W; And/or described die pressing is undertaken by following operational approach: by compressing for described mixed-powder, then heat up, sinter molding; The speed of described intensification is 1 DEG C/min ~ 4 DEG C/min; The temperature of described sintering is 350 DEG C ~ 360 DEG C; The temperature retention time of described sintering is 2 hours ~ 3 hours.
6. the mesoporous calcium magnesium silicate/polyether-ether-ketone composite material obtained by the preparation method described in claim 4 or 5.
7. the application of mesoporous calcium magnesium silicate/polyether-ether-ketone composite material as claimed in claim 6 in bone repair.
8. a preparation method for bone repair, is characterized in that, it comprises the steps:, by raw material Homogeneous phase mixing, to obtain mixed-powder, and described raw material is mesoporous calcium magnesium silicate as claimed in claim 3 and polyether-ether-ketone; Then described mixed-powder is mixed with dehydrated alcohol, ultrasonic disperse, then at 58 DEG C ~ 62 DEG C, evaporate dehydrated alcohol, obtain composite powder; Described composite powder is carried out molding sintering molding in the mould of bone repair product, to obtain final product; Wherein, the consumption of described mesoporous calcium magnesium silicate accounts for the 20wt% ~ 40wt% of raw material gross weight, and the consumption of described polyether-ether-ketone accounts for the 60wt% ~ 80wt% of raw material gross weight; The particle diameter of described polyether-ether-ketone is 10 μm ~ 20 μm.
9. preparation method as claimed in claim 8, it is characterized in that, the particle diameter of described polyether-ether-ketone powder is 10 μm ~ 15 μm; And/or the temperature of described evaporation dehydrated alcohol is 60 DEG C; And/or the time of described ultrasonic disperse is 15min ~ 30min, the power of described ultrasonic disperse is 60W ~ 90W; And/or the mould of described bone repair product is the mould of spinal bone dummy or the mould of tooth implant; And/or described molding sintering molding is undertaken by following operational approach: by compressing for described mixed-powder, then heat up, sinter molding; The speed of described intensification is 1 DEG C/min; The temperature of described sintering is 350 DEG C ~ 360 DEG C; The temperature retention time of described sintering is 2 hours ~ 3 hours; And/or, after described machine-shaping, also carry out surface coarsening process, described surface coarsening process is carried out in the steps below: use surface coarsening machine, with mesoporous calcium silicates magnesium granules, surface coarsening is carried out to the block that described machine-shaping obtains, form to described block surface the porous surface that aperture is 100 μm ~ 200 μm; The particle diameter of described mesoporous calcium magnesium silicate is 100 μm ~ 500 μm.
10. the bone repair obtained by preparation method described in claim 8 or 9.
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