CN109095446A - A kind of biophasic calcium phosphate ceramic material and preparation method thereof - Google Patents
A kind of biophasic calcium phosphate ceramic material and preparation method thereof Download PDFInfo
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- CN109095446A CN109095446A CN201810980246.8A CN201810980246A CN109095446A CN 109095446 A CN109095446 A CN 109095446A CN 201810980246 A CN201810980246 A CN 201810980246A CN 109095446 A CN109095446 A CN 109095446A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention provides a kind of biophasic calcium phosphate ceramic materials and preparation method thereof.The biophasic calcium phosphate ceramic material, which is characterized in that its preparation step includes: to be boiled using hairtail as raw material, removes organic matter, and resulting fish-bone is dry, and calcined fish-bone is immersed in Na by calcining4P2O7·10H2It in O solution, takes out, dry, grinding obtains the biphasic calcium phosphate material containing hydroxyapatite and beta-calcium phosphate.Raw material sources of the present invention are abundant, can get in major fishery market, and preparation cost is low, and the biphasic calcium phosphate prepared does not have more impurity, can control the component ratio of biophasic calcium phosphate ceramic material by adjusting soak concentration just.The raw material natural environmental-protective that the invention uses, the biphasic calcium phosphate prepared are more pure.
Description
Technical field
The present invention relates to biomedical ceramics fields, specifically, being a kind of preparation side of biophasic calcium phosphate ceramic material
Method.
Background technique
Failure, the damage of tissue and organ are one of main problems that clinical medicine faces.The whole world is every year because each
Fracture caused by kind reason and bone defect injury number reach several ten million.In China, injury number is also being quicklyd increase, according to civil administration
Section report, bone defect patient nearly 3,000,000.Traditional bone renovating material can not meet the requirement of contemporary clinical medicine, more
Carry out more researcher and finds that the degradation rate of the biophasic calcium phosphate ceramic material containing hydroxyapatite and beta-calcium phosphate can be with
Promote the formation of area of new bone.
Domestic and foreign scholars prepare biphasic calcium phosphate using the method for the commercial synthesis such as wet process, chemical precipitation method, these biographies
New impurity can be introduced in the product that the preparation method of system obtains, preparation process is complicated, at high cost.
Summary of the invention
The object of the present invention is to provide a kind of cheap, preparation sides of the simple biophasic calcium phosphate ceramic material of process
Method.
In order to achieve the above object, the present invention provides a kind of biophasic calcium phosphate ceramic materials, which is characterized in that it is prepared
Step includes: to be boiled using hairtail as raw material, removes organic matter, and resulting fish-bone is dry, calcining, by calcined fish-bone
It is immersed in Na4P2O7·10H2It in O solution, takes out, dry, grinding obtains the two-phase phosphorus containing hydroxyapatite and beta-calcium phosphate
Sour calcium material.
Preferably, the partial size of the biphasic calcium phosphate material is 300-500nm.
The present invention also provides the preparation methods of above-mentioned biophasic calcium phosphate ceramic material, which is characterized in that including following
Step:
A, it boils: hairtail is boiled, remove the organic matter and grease stain on hairtail vertebral bony surfaces;
B, drying: the resulting fish-bone of step A is subsequently placed in drying box dry;
C, it is sintered: fish-bone of the step B after dry being placed in Muffle furnace and is calcined;
D, it impregnates: the calcined fish-bone of step C is immersed in Na4P2O7·10H2It in O solution, then takes out, is put into drying
It is dried in case;
E, it grinds: fish-bone sample of the step D after dry being placed in mortar, powder is ground into.
Preferably, drying box temperature programmed control is 15-20 minutes a length of when dry at 65-75 DEG C in the step B.
Preferably, for Muffle furnace temperature programmed control at 850-950 DEG C, heating rate is 4-6 DEG C/min in the step C, is protected
The warm time is 1-2 hours.
Preferably, Na in the step D4P2O7·10H2The concentration of O solution is 0.02mol/L-0.1mol/L.
Most preferably, Na in the step D4P2O7·10H2The concentration of O solution is 0.06mol/L.
Preferably, the soaking process in the step D carries out in drying box, and temperature is set as 65-75 DEG C, dry 20-
30 hours.
Preferably, the biphasic calcium phosphate material contains the hydroxy-apatite of circular beta-calcium phosphate particle and corynebacterium
Stone crystal whisker.
Raw material used in the present invention is band fish-bone, and the acquisition of raw material is extremely convenient, by boiling removal organic matter and oil
Then stain is dried, then the band fish-bone after drying is placed in the calcining of Muffle furnace high temperature, and calcined fish-bone sample is immersed in not
With the Na of concentration4P2O7·10H2In O solution, it is put into drying in drying box, calcined fish-bone is finally worn into powder with mortar
For characterize in product whether the biophasic calcium phosphate ceramic material containing hydroxyapatite and beta-calcium phosphate mixture.
Compared with prior art, the beneficial effects of the present invention are:
The present invention uses Na4P2O7·10H2O solution impregnates fish-bone to extract biophasic calcium phosphate ceramic material, this preparation
Method is cheap, and process is simple, and the product extracted is purer, can control biphasic calcium phosphate only by adusting soak concentration
The component ratio of ceramic material.
Raw material sources of the present invention are abundant, can get in major fishery market, preparation cost is low, the two-phase prepared
Calcium phosphate does not have more impurity, can control the component ratio of biophasic calcium phosphate ceramic material by adjusting soak concentration just.This hair
The bright raw material natural environmental-protective used, the biphasic calcium phosphate prepared are more pure.
Detailed description of the invention
Fig. 1 is the band fish-bone picture calcined at 900 DEG C.
Fig. 2 is band fish-bone in 700 DEG C, 800 DEG C and 900 DEG C calcined X-ray diffractogram (Na4P2O7·10H2O solution
Concentration is 0.06mol/L).
Fig. 3 is 900 DEG C of calcined Na being immersed under various concentration with fish-bone4P2O7·10H2X-ray in O solution
Diffraction pattern.
Fig. 4 is the infared spectrum with fish-bone under 900 DEG C of calcination temperatures.
Fig. 5 is the microsctructural photograph with fish-bone at 900 DEG C.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of preparation method of biophasic calcium phosphate ceramic material, specific steps are as follows:
Raw material: fishbone of hairtail, the place of production: being distributed mainly on Western Pacific and the Indian Ocean, the Huanghai Sea, the East Sea, the Bohai Sea in China
Until the South Sea is all distributed.
It boils: hairtail is placed in boiling water about three hours, repeat this operation 3-4 times, completely remove and be attached to hairtail ridge
The organic substance and grease stain of vertebral surface.
It is dry: next processed fish-bone to be placed in thermostatic drying chamber, temperature is transferred to 70 degrees Celsius, dry 15-
20 minutes, to remove remaining moisture on fish-bone.
Sintering: after the completion of dry, fish-bone is placed in Muffle furnace and is calcined, then starts setting up program, temperature programmed control is 900
DEG C, heating rate is 5 DEG C/min, and soaking time is 1-2 hours, and atmosphere is air.
Impregnate: it is respectively 0.02mol/L, 0.04mol/L, 0.06mol/ that calcined fish-bone sample, which is immersed in concentration,
L, the Na of 0.08mol/L, 0.1mol/L4P2O7·10H212 hours in O solution, then takes out and be put into drying box dry, temperature
Degree is set as 70 DEG C, drying 24 hours;
Grinding: the fish-bone sample after immersion and drying is placed in mortar, powder is ground into, as contains hydroxyapatite
With the biphasic calcium phosphate material of beta-calcium phosphate.
Embodiment 2
A kind of preparation method of biophasic calcium phosphate ceramic material is similar to embodiment 1, and difference is: in calcining step, temperature
Degree is 700 DEG C and 800 DEG C.
Embodiment 3: the constituent analysis in calcined product
In order to understand fish-bone sample at being grouped as, using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy
(FTIR) calcined product in embodiment 1 and embodiment 2 is analyzed.
Contain hydroxyapatite and beta-calcium phosphate phase in calcined band fish-bone sample from can be seen that in XRD diagram, and
As the temperature rises, the diffraction maximum of hydroxyapatite reduces, and the diffraction maximum of beta-calcium phosphate increases instead, this also means that β-phosphorus
The relative amount of sour calcium gradually increases, as shown in Figure 2.From here it may be concluded that temperature is to influence biphasic calcium phosphate
One of an important factor for middle hydroxyapatite and beta-calcium phosphate component ratio.
Under mutually synthermal (900 DEG C), calcined fish-bone sample is immersed in various concentration, and the result obtained is also to have
Difference.From 0.04mol/L to 0.08mol/L within the scope of this, it can be seen that when soak concentration is 0.06mol/L
It waits, the diffraction peak intensity of beta-calcium phosphate is clearly more prominent with respect to the peak intensity of hydroxyapatite, as shown in Figure 3.Therefore, at five
In concentration, effect is best when soak concentration is 0.06mol/L.
The method for carrying out constituent analysis to calcined product in embodiment 1 using Fourier transform infrared spectroscopy is as follows: using
670 spectrometer of Agilent Cary is in 4000-400cm-1With 1cm in range-1Resolution ratio carried out under absorbance patterns, will
Sample and anhydrous potassium bromide are mixed with the ratio of 1:50 and are pressed into thin rounded flakes and analyzed.It can be found that leaching from infared spectrum
Bubble liquid concentration occur the characteristic peak of apparent beta-calcium phosphate when 0.04-0.08mol/L, this be also from XRD diagram only
The reason of analyzing these three concentration, as shown in Figure 4.
Embodiment 4: the microstructure and morphology analysis of calcined product
It is in pure white after 1 gained band fish-bone calcining of embodiment, as shown in Figure 1.Using scanning electron microscope it can be observed that circle
Beta-calcium phosphate particle and a little corynebacterium hydroxyapatite crystal whisker, particle size is between 300-500nm, such as Fig. 5 institute
Show.
Fig. 5 represents soak concentration as the micrograph under 0.04,0.06,0.08mol/L.Beta-calcium phosphate in a and c figure
Particle is smaller, and arrangement is compact, is easy to happen agglomeration, and the boundary in b figure between crystal grain is than more visible, convenient
Fluid is transmitted by hole.
The embodiment of the present invention combination attached drawing is illustrated above, those skilled in the art are without prejudice to the present invention
The present invention can be modified or be changed under the premise of creative spirit, these equivalent variation or replacement are all contained in the application
In claim limited range.
Claims (9)
1. a kind of biophasic calcium phosphate ceramic material, which is characterized in that its preparation step includes: to be boiled, gone using hairtail as raw material
Except organic matter, resulting fish-bone is dry, calcined fish-bone is immersed in Na by calcining4P2O7·10H2In O solution, take out,
Dry, grinding obtains the biphasic calcium phosphate material containing hydroxyapatite and beta-calcium phosphate.
2. biophasic calcium phosphate ceramic material as described in claim 1, which is characterized in that the grain of the biphasic calcium phosphate material
Diameter is 300-500nm.
3. the preparation method of biophasic calcium phosphate ceramic material of any of claims 1 or 2, which comprises the following steps:
A, it boils: hairtail is boiled, remove the organic matter and grease stain on hairtail vertebral bony surfaces;
B, drying: the resulting fish-bone of step A is subsequently placed in drying box dry;
C, it is sintered: fish-bone of the step B after dry being placed in Muffle furnace and is calcined;
D, it impregnates: the calcined fish-bone of step C is immersed in Na4P2O7·10H2It in O solution, then takes out, is put into drying box
It is dried;
E, it grinds: fish-bone sample of the step D after dry being placed in mortar, powder is ground into.
4. the preparation method of biophasic calcium phosphate ceramic material as claimed in claim 3, which is characterized in that in the step B
Drying box temperature programmed control is 15-20 minutes a length of when dry at 65-75 DEG C.
5. the preparation method of biophasic calcium phosphate ceramic material as claimed in claim 3, which is characterized in that in the step C
For Muffle furnace temperature programmed control at 850-950 DEG C, heating rate is 4-6 DEG C/min, and soaking time is 1-2 hours.
6. the preparation method of biophasic calcium phosphate ceramic material as claimed in claim 3, which is characterized in that in the step D
Na4P2O7·10H2The concentration of O solution is 0.02mol/L-0.1mol/L.
7. the preparation method of biophasic calcium phosphate ceramic material as claimed in claim 3, which is characterized in that in the step D
Na4P2O7·10H2The concentration of O solution is 0.06mol/L.
8. the preparation method of biophasic calcium phosphate ceramic material as claimed in claim 3, which is characterized in that in the step D
Soaking process carried out in drying box, temperature is set as 65-75 DEG C, 20-30 hours dry.
9. the preparation method of biophasic calcium phosphate ceramic material as claimed in claim 3, which is characterized in that the two-phase phosphoric acid
Calcium material contains the hydroxyapatite crystal whisker of circular beta-calcium phosphate particle and corynebacterium.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113952504A (en) * | 2021-10-29 | 2022-01-21 | 华南理工大学 | Selenium-doped coral/hydroxyapatite scaffold and preparation method thereof |
CN115300668A (en) * | 2022-06-24 | 2022-11-08 | 上海市东方医院(同济大学附属东方医院) | Bi-phase calcium phosphate porous biological ceramic bone scaffold material derived from pomfret bones and preparation method and application thereof |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113952504A (en) * | 2021-10-29 | 2022-01-21 | 华南理工大学 | Selenium-doped coral/hydroxyapatite scaffold and preparation method thereof |
CN113952504B (en) * | 2021-10-29 | 2022-12-16 | 华南理工大学 | Selenium-doped coral/hydroxyapatite scaffold and preparation method thereof |
CN115300668A (en) * | 2022-06-24 | 2022-11-08 | 上海市东方医院(同济大学附属东方医院) | Bi-phase calcium phosphate porous biological ceramic bone scaffold material derived from pomfret bones and preparation method and application thereof |
CN115300668B (en) * | 2022-06-24 | 2024-01-23 | 上海市东方医院(同济大学附属东方医院) | Pomfret bone-derived biphasic calcium phosphate porous bioceramic bone scaffold material, and preparation method and application thereof |
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