CN104399126A - Preparation method of nano composite material through blending carbonate-ion-doped hydroxy apatite and polymethyl methacrylate - Google Patents
Preparation method of nano composite material through blending carbonate-ion-doped hydroxy apatite and polymethyl methacrylate Download PDFInfo
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- CN104399126A CN104399126A CN201410624393.3A CN201410624393A CN104399126A CN 104399126 A CN104399126 A CN 104399126A CN 201410624393 A CN201410624393 A CN 201410624393A CN 104399126 A CN104399126 A CN 104399126A
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Abstract
The invention discloses a preparation method of a nano composite material through blending carbon-ion-doped hydroxy apatite and polymethyl methacrylate, and belongs to the field of bio-mimetic bone materials. The carbonate-ion-doped hydroxy apatite is successfully prepared through a chemical deposition method: a calcium nitrate solution and a phosphate solution are taken as the reactants, then sodium bicarbonate is added, and finally the pH value is adjusted to prepare the target product. On the basis of previous researches, a Hakke torque rheometer is used to blend carbonate-ion-doped hydroxy apatite and polymethyl methacrylate so as to prepare the composite bone substitute material. The preparation is simple and practical, the reaction period is not long, the raw material cost is low, and the method is suitable for industrial production. Moreover, the provided material can improve the rehabilitation treatment level and the life quality of patients, and provides precise and effective references for the diagnosis on human bone diseases.
Description
Technical field
The invention belongs to bionic bone material technical field, particularly the preparing technical field of blended nano composite material.
Background technology
Hydroxyapatite (Hydroxyapatite, HAP) is the topmost inorganic composition of human skeleton and tooth, because HAP has good biological activity and bone conductibility, after in the implanted human body of HAP, and Ca
2+and P
3+to dissociate the surface of HAP, thus to be systemically absorbed, and grow the tissue made new advances.Studies have found that the crystal grain of HAP is thinner, its biological activity is higher.The crystallographic system of HAP is hexagonal crystal system, and its proportion is 3.08, and mohs hardness is 5.Pure sample HAP powder is white, but natural HAP to be mingled with brown, yellow or green slightly.HAP also can synthesize by artificial mode, and HAP is widely used in bone tissue restoration.Such as, utilize the good biocompatibility of nanometer hydroxyapatite crystallite, for the preparation of the liquid chromatograph separating medium being separated different kind organism molecule.
In addition, people also find that nano level hydroxyapatite material has and has good inhibitory action to cancerous cell, nano-grade hydroxy apatite has good targeting simultaneously, and in conjunction with above-mentioned two dot characteristics, nano-grade hydroxy apatite can well apply to the development of cancer therapy drug.
The method presently preparing hydroxyapatite is a lot, is mainly divided into solid phase method and the large class of liquid phase method two.The nanoscale of different shape can be prepared, the nanoparticle of such as almost spherical and needle-like, nanometer rods (fiber, line), layered nano-structure, flower-like nanostructure, bowknot shape nanostructured and meso-porous nano structure etc. in existing document.
Hydroxyapatite has fine biocompatibility, at biomedical sector, there is boundless application prospect, but in order to make the performance of hydroxyapatite more close to the bony structures in human body, we can carry out modification to hydroxyapatite nanoparticle, adulterate some nontoxic ions of entering in hydroxyapatite, such as carbanion.The interpolation of carbanion, can change the crystal structure of hydroxyapatite, and its degree of crystallinity is reduced, and increases the dissolubility of crystallization, promotes its degraded in vivo, improves its biological activity.Patent CN200910103200 discloses the preparation method of carbanion doped hydroxyapatite nano-powder, pour in autoclave after a certain amount of calcium nitrate aqueous solution is mixed homogeneously by Ca/P atomic ratio 1.65 ~ 1.72 with a certain amount of aqueous dibasic potassium phosphate solution, under carbon dioxide atmosphere, thing generation hydro-thermal reaction in still is made to reactor heating, after having reacted, carry out sucking filtration, rinse, oven dry, obtain carbonate-containing hydroxylapatite powder.It is comparatively loaded down with trivial details that this technology prepares to get up process, and workload is comparatively large, and by contrast, the present invention is simple to operate, materials economy.
In blended nanometer hydroxyapatite and polymethyl methacrylate composite bone substitution material, hydroapatite particles is dispersed in macromolecule matrix uniformly, thus obtains better performance.As patent CN200910229602 discloses a kind of preparation method of hydroxyapatite composite material, powdery hydroxyapatite is placed in ultrasound wave pretreatment, then silane coupler is added by a certain amount of mass ratio of hydroxyapatite/silane coupler, add solvent and polymerization inhibitor again, adjust ph 3-4, stirs a period of time and then washs under uniform temperature, dry, obtain the hydroxyapatite of surface modification, for subsequent use; Again with methyl methacrylate (MMA) for monomer, add initiator, complexant, catalyst, add solvent, stir a period of time, continue reaction, then dissolve by precipitant precipitation and oxolane and carry out purification, then through washing, drying, obtain colourless polymethyl methacrylate (PMMA) for subsequent use; Then take PMMA as initiator, with the hydroxyapatite of surface modification for monomer carries out graft reaction, synthesize polymethyl methacrylate/hydroxyapatite composite material in the mode being grafted to surface, product, through washing, drying, obtains PMMA/HAP composite powder.This technology preparation is got up, and quantities is large, and raw material is more expensive.
Summary of the invention
Be directed to the imperfection of current carbanion doped hydroxyapatite and the blended nano composite material technology of polymethyl methacrylate, the present invention proposes a kind of new route of synthesis, the reaction of this course of reaction synthesis requires low, reaction time is not long, the cost of whole experiment is not high, meets the requirement of Green Chemistry completely.
Step of the present invention is as follows:
1) carbanion doped hydroxyapatite is prepared: under magnetic stirring, first aqueous phosphatic is added dropwise in calcium nitrate aqueous solution, and then add sodium bicarbonate aqueous solution, after adjusting pH value to 8 ~ 12 of mixed liquor, after stirring, obtain milk and carry out sucking filtration, washing, oven dry, namely obtain carbanion doped hydroxylapatite powder;
2) carbanion doped hydroxyapatite and the blended nano composite material of polymethyl methacrylate is prepared: carbanion doped hydroxylapatite powder and polymethyl methacrylate are carried out melt blending on banbury, through tabletting, obtain carbanion doped hydroxyapatite and the blended nano composite material of polymethyl methacrylate.
Together the hydroxyapatite that the present invention adopts above method to make is formed by much tiny nano whiskers particle packing, the carbanion containing controlled amounts in product.The present invention not only process is simple, and reaction time is not long, and cost of material is low, be applicable to commercial production, and this invention is for improving rehabilitation level, and improve minimal invasive treatment's level and quality of life, the diagnosis for mankind's osteopathia provides foundation accurately and effectively.
In addition, in order to realize the abundant reaction of raw material, when mixing in step 1) of the present invention, the mol ratio of the P in described aqueous phosphatic and the Ca in calcium nitrate aqueous solution is 1:1.67.
In step 1), described phosphate is the salt containing phosphate radical or hydrogen phosphate.Phosphate is as the main source of P element in hydroxyapatite.
Salt containing phosphoric acid hydrogen radical ion is sodium ammonium biphosphate or diammonium phosphate.Sodium ammonium biphosphate or diammonium phosphate low price, soluble in water, sufficient reacting.
Bake out temperature in step 1) is 60 ~ 100 DEG C.Dry at this temperature, remove ionized water, by volatile Impurity removal.
In order to the fully effective removal ionized water of energy volatile impurity, in step 1), drying time is 3 ~ 5h.
Step 2) in carbanion doped hydroxylapatite powder be 1 ~ 5:100 with the mixing quality ratio of polymethyl methacrylate.Nano composite material best performance after blended under this ratio.
When melt blending, the temperature of described carbanion doped hydroxylapatite powder and polymethyl methacrylate is 210 DEG C, and banbury rotating speed is 50 ~ 100r/min.Better blended under this temperature and rotating speed.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the carbonic acid prepared by the embodiment of the present invention 1 with ion doping hydroxy apatite powder.
Fig. 2 is the transmission electron microscope photo of the carbonic acid prepared by the embodiment of the present invention 4 with ion doping hydroxy apatite powder.
Fig. 3 is the XRD spectra of the carbonic acid prepared by the embodiment of the present invention 1 ~ 4 with ion doping hydroxy apatite powder.
Fig. 4 is the FTIR spectrogram of the carbonic acid prepared by the embodiment of the present invention 1 ~ 4 with ion doping hydroxyapatite stone powder body.
Fig. 5 is carbanion doped hydroxyapatite prepared by the embodiment of the present invention 5 ~ 7 and the variation relation figure of the impact strength of different carbonate doping in the blended nano composite material of polymethyl methacrylate and composite.
Fig. 6 is carbanion doped hydroxyapatite prepared by example 5 ~ 7 of the present invention and the variation relation figure of the hardness of different carbonate doping in the blended nano composite material of polymethyl methacrylate and composite.
Detailed description of the invention
In order to make the advantage of technical characterstic of the present invention, goal of the invention and scheme more directly perceived, in conjunction with following specific embodiment, the present invention program is described in further detail.Following examples of implementation implement under the scheme of the present invention, and protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
The lime nitrate of 6g is dissolved in the deionized water of certain volume, carries out stirring fully for 10 minutes with magnetic stirring apparatus, form calcium nitrate aqueous solution.
Under indoor temperature and condition of normal pressure, 2.9588g phosphate is dissolved in deionized water, and is stirred to and dissolves completely, form phosphate solution.
Under indoor temperature and condition of normal pressure, 4g sodium bicarbonate is dissolved in deionized water, and is stirred to and dissolves completely, form carbanion solution.
Under magnetic agitation action condition, the phosphate solution prepared slowly is added dropwise in the solution of the lime nitrate prepared.After being added dropwise to complete, under magnetic agitation action condition, the carbanion solution configured slowly is added in above-mentioned mixed liquor.After forming suspension, regulate pH to 10 ~ 11 with ammonia, and Keep agitation 1h.After stirring terminates, carry out sucking filtration to precipitation, at least use deionized water rinse more than 3 times, extracting waste precipitation is dried.
Finally can obtain white powder, be the powder body (CHAP) of carbonate doped hydroxyapatite.
The white powder made be can be observed its form under transmission electron microscope, and as shown in Figure 1, the content of its carbanion is 5% as seen.
Embodiment 2:
The lime nitrate of 6g is dissolved in the deionized water of certain volume, carries out stirring fully for 10 minutes with magnetic stirring apparatus, form the solution of lime nitrate.
Under indoor temperature and condition of normal pressure, 2.9588g phosphate is dissolved in deionized water, and is stirred to and dissolves completely, form phosphate solution.
Under indoor temperature and condition of normal pressure, 5g sodium bicarbonate is dissolved in deionized water, and is stirred to and dissolves completely, form phosphate solution.
Under magnetic agitation action condition, the phosphate solution prepared slowly is added dropwise in the solution of the lime nitrate prepared.After being added dropwise to complete, under magnetic agitation action condition, the carbanion solution configured slowly is added in above-mentioned mixed liquor.After forming suspension, regulate pH to 10 ~ 11 with ammonia, and Keep agitation 1h.After stirring terminates, sucking filtration is carried out to precipitation, at least use deionized water rinse more than 3 times.The white precipitate obtained is dried.
Finally can obtain white powder, powder is a kind of powder body (CHAP) of carbonate doped hydroxyapatite.
Embodiment 3
The lime nitrate of 6g is dissolved in the deionized water of certain volume, carries out stirring fully for 10 minutes with magnetic stirring apparatus, form the solution of lime nitrate.
Under indoor temperature and condition of normal pressure, 2.9588g phosphate is dissolved in deionized water, and is stirred to and dissolves completely, form phosphate solution.
Under indoor temperature and condition of normal pressure, 6g sodium bicarbonate is dissolved in deionized water, and is stirred to and dissolves completely, form phosphate solution.
Under magnetic agitation action condition, the phosphate solution prepared slowly is added dropwise in the solution of the lime nitrate prepared.After being added dropwise to complete, under magnetic agitation action condition, the carbanion solution configured slowly is added in above-mentioned mixed liquor.After forming suspension, regulate pH to 10 ~ 11 with ammonia, and Keep agitation 1h.After stirring terminates, sucking filtration is carried out to precipitation, at least use deionized water rinse more than 3 times.The white precipitate obtained is dried.
Finally can obtain white powder, powder is a kind of powder body (CHAP) of carbonate doped hydroxyapatite.
Embodiment 4
The lime nitrate of 6g is dissolved in the deionized water of certain volume, carries out stirring fully for 10 minutes with magnetic stirring apparatus, form the solution of lime nitrate.
Under indoor temperature and condition of normal pressure, 2.9588g phosphate is dissolved in deionized water, and is stirred to and dissolves completely, form phosphate solution.
Under indoor temperature and condition of normal pressure, 7g sodium bicarbonate is dissolved in deionized water, and is stirred to and dissolves completely, form phosphate solution.
Under magnetic agitation action condition, the phosphate solution prepared slowly is added dropwise in the solution of the lime nitrate prepared.After being added dropwise to complete, under magnetic agitation action condition, the carbanion solution configured slowly is added in above-mentioned mixed liquor.After forming suspension, regulate pH to 10 ~ 11 with ammonia, and Keep agitation 1h.After stirring terminates, sucking filtration is carried out to precipitation, at least use deionized water rinse more than 3 times.The white precipitate obtained is dried.
Finally can obtain white powder, be a kind of powder body (CHAP) of carbonate doped hydroxyapatite.
The white powder made be can be observed its form under transmission electron microscope, and as shown in Figure 2, the content of its carbanion is 9% as seen.
Phosphate above in each embodiment or employing sodium ammonium biphosphate, or adopt diammonium phosphate.
The carbanion doped hydroxylapatite powder that above embodiment 1 to 4 is prepared respectively is carried out XRD detection, the changes in intensity values after 2 times of X-ray angle of incidence and diffraction of Fig. 3: embodiment 1 to 4 has been prepared respectively and disperseed comparatively uniform carbanion doped hydroxylapatite powder and the blended nano composite material of polymethyl methacrylate.
The FTIR figure of the carbanion doped hydroxylapatite powder prepared respectively from the embodiment 1 to 4 of Fig. 4: along with the increase of carbonate content, the enhancing of Partial Feature peak, when carbonate content about more than 9.03% time, Partial Feature peak weakens.
Embodiment 5
Take the 1g carbanion doped hydroxylapatite powder for preparing in example 3 and 100g polymethyl methacrylate carries out melt blending, 210 DEG C, 60 rpms on Haake banbury, extruder temperature is respectively 210,210,210 DEG C; Carry out tabletting again, make 20 battens.Finally obtain intermingling material, material is carbanion doped hydroxyapatite and the blended nano composite material of polymethyl methacrylate.
Embodiment 6
Take the 3g carbanion doped hydroxylapatite powder for preparing in example 3 and 100g polymethyl methacrylate carries out melt blending, 210 DEG C, 60 rpms on Haake banbury, extruder temperature is respectively 210,210,210 DEG C; Carry out tabletting again, make 20 battens.Finally obtain intermingling material, material is carbanion doped hydroxyapatite and the blended nano composite material of polymethyl methacrylate.
Embodiment 7
Take the 5g carbanion doped hydroxylapatite powder for preparing in example 3 and 100g polymethyl methacrylate carries out melt blending, 210 DEG C, 60 rpms on Haake banbury, extruder temperature is respectively 210,210,210 DEG C; Carry out tabletting again, make 20 battens.Finally obtain intermingling material, material is carbanion doped hydroxyapatite and the blended nano composite material of polymethyl methacrylate.
Fig. 5 reflects the impact strength of carbanion doped hydroxyapatite prepared by embodiment 5 ~ 7 and the blended nano composite material of polymethyl methacrylate.The cantilever beam impact strength of carbanion doped hydroxyapatite and polymethyl methacrylate co-mixing system presents the rear downward trend that first rises as seen from Figure 5.When carbanion doped hydroxylapatite powder content is about 1%, impact strength reaches the highest.
Fig. 6 reflects the hardness of carbanion doped hydroxyapatite prepared by embodiment 5 ~ 7 and the blended nano composite material of polymethyl methacrylate.The hardness of carbanion doped hydroxyapatite and polymethyl methacrylate co-mixing system presents the trend first declining and rise as seen from Figure 6.When carbanion doped hydroxyapatite mass fraction is more 1%, hardness reaches minimum.
Claims (8)
1. the preparation method of a carbanion doped hydroxyapatite and the blended nano composite material of polymethyl methacrylate is characterized in that comprising the following steps:
1) carbanion doped hydroxylapatite powder is prepared: under magnetic stirring, first aqueous phosphatic is added dropwise in calcium nitrate aqueous solution, and then add sodium bicarbonate aqueous solution, after adjusting pH value to 8 ~ 12 of mixed liquor, after stirring, obtain milk and carry out sucking filtration, washing, oven dry, namely obtain carbanion doped hydroxylapatite powder;
2) carbanion doped hydroxyapatite and the blended nano composite material of polymethyl methacrylate is prepared: carbanion doped hydroxylapatite powder and polymethyl methacrylate are carried out melt blending on banbury, through tabletting, obtain carbanion doped hydroxyapatite and the blended nano composite material of polymethyl methacrylate.
2. preparation method according to claim 1, when it is characterized in that mixing in described step 1), the mol ratio of the P in described aqueous phosphatic and the Ca in calcium nitrate aqueous solution is 1:1.67.
3. preparation method according to claim 1, it is characterized in that in described step 1), described phosphate is the salt containing phosphate radical or hydrogen phosphate.
4. preparation method according to claim 3, is characterized in that the salt containing phosphoric acid hydrogen radical ion is sodium ammonium biphosphate or diammonium phosphate.
5. preparation method according to claim 1, is characterized in that the bake out temperature in described step 1) is 60 ~ 100 DEG C.
6. preparation method according to claim 1 or 5, is characterized in that in described step 1), drying time is 3 ~ 5h.
7. preparation method according to claim 1, is characterized in that described step 2) in carbanion doped hydroxyapatite be 1 ~ 5:100 with the mixing quality ratio of polymethyl methacrylate.
8. preparation method according to claim 7, it is characterized in that when melt blending, the temperature of described carbanion doped hydroxyapatite and polymethyl methacrylate is 210 DEG C, and banbury rotating speed is 50 ~ 100r/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105137509A (en) * | 2015-08-20 | 2015-12-09 | 扬州大学 | Method for smearing biological activity hydroxy apatite transparent film on different optical element substrates |
| CN106430133A (en) * | 2016-04-29 | 2017-02-22 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Method for preparing carbonate-containing hydroxyapatite material applicable to radiation dose meter |
| CN108529580A (en) * | 2018-05-18 | 2018-09-14 | 南京农业大学 | A kind of enrichment hydroxyapatite of carbonate, the equipment for preparing it, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028146A (en) * | 2011-09-29 | 2013-04-10 | 深圳兰度生物材料有限公司 | Reinforcement medical composite material and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028146A (en) * | 2011-09-29 | 2013-04-10 | 深圳兰度生物材料有限公司 | Reinforcement medical composite material and method for preparing same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105137509A (en) * | 2015-08-20 | 2015-12-09 | 扬州大学 | Method for smearing biological activity hydroxy apatite transparent film on different optical element substrates |
| CN106430133A (en) * | 2016-04-29 | 2017-02-22 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Method for preparing carbonate-containing hydroxyapatite material applicable to radiation dose meter |
| CN108529580A (en) * | 2018-05-18 | 2018-09-14 | 南京农业大学 | A kind of enrichment hydroxyapatite of carbonate, the equipment for preparing it, preparation method and application |
| CN108529580B (en) * | 2018-05-18 | 2021-06-11 | 南京农业大学 | Carbonate-enriched hydroxyapatite, and equipment, preparation method and application thereof |
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Application publication date: 20150311 |