CN100491288C - Preparation method of nano porous biologic ceramics - Google Patents
Preparation method of nano porous biologic ceramics Download PDFInfo
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- CN100491288C CN100491288C CNB2005100216204A CN200510021620A CN100491288C CN 100491288 C CN100491288 C CN 100491288C CN B2005100216204 A CNB2005100216204 A CN B2005100216204A CN 200510021620 A CN200510021620 A CN 200510021620A CN 100491288 C CN100491288 C CN 100491288C
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Abstract
The present invention discloses the preparation process and apparatus for nanometer porous bioceramic. Slurry with nanometer structure is synthesized and centrifugally separated to form thick slurry; the thick slurry is added with foaming agent and formed into the initial blank; the initial blank is plasticized, and microwave sintered at 800-1400 deg.c for 0.5-30 min in the temperature raising rate of 25-200 deg.c/min; and the sintered product is cooled in the temperature lowering rate of 50-200 deg.c/min to room temperature to obtain the bioceramic product with nanometer structure. The preparation process is fast, simple and cheap, and the prepared bioceramic material has high bioactivity and high mechanical performance.
Description
One. technical field
The present invention relates to a kind of preparation method of nano porous biologic ceramics.
Two. background technology
The preparation of ceramics sample relates to synthetic, dry, homogenate, injection molding, moulding, many processes such as sintering, wherein powder be synthesized to the reunion that unavoidably there is powder in drying process, sintering process exists the growth of crystal grain.
At present, the preparation of all biological ceramics samples all is that powder can make after drying and be rendered as nano level particle agglomeration in solution is micron order even bigger particle from synthetic dried powder; The sintering of sample adopts the retort furnace sintering more in addition, and the powder that obtains after being characterized in variously synthesizing forms densification or the first base substrate of porous by different forming methods, is placed on high temperature sintering more than at least 2 hours through plastic removal.The gained result is that the crystal grain of material is bigger, and biological activity and mechanical property are relatively poor.For the biologic activity that improves material must suitably reduce sintering temperature and shorten sintering time, at this moment the intensity of material often be cannot say for sure to demonstrate,prove.And, the grain-size that makes material is become big for the intensity that improves material raising sintering temperature that adopts usually and the method that prolongs sintering time, and degree of crystallinity increases, and biologic activity descends.Not only energy waste is big for the long-time sintering of high temperature, also may cause burn-off phenomenon, causes the physicochemical property of material to descend.
Microwave sintering is to utilize in the loss of microwave electromagnetic field medium to make pottery and matrix material integral body thereof be heated to sintering temperature and realize the Fast Sintering new technology of densification.Compare with normal sintering, microwave sintering has rapid heating, Fast Sintering, high-effect, energy-efficient and improve material structure, improve series of advantages such as material property, this homogeneous heating, sintering time weak point, the advantage that energy consumption is low makes this new technology developed rapidly at present, by 2004, people successfully prepared Al with microwave sintering
2O
3, ZrO
2, B
4C, Al
2O
3Many different types of structure nano stupaliths such as-TiC.But the microwave sintering about biological ceramics is then rarely reported.
Cai Jie etc. have obtained the fine and close hydroxyapatite of density greater than 98% theoretical density, its grain-size average out to 300nm in " postgraduate of Chinese Academy of Sciences wall bulletin " the 2nd phase in 1996 " the microwave Fast Sintering research of hydroxyapatite ".Yang Yunzhi etc. are in " material Leader " the 14th phase in 2000 " microwave and normal sintering hydroxyapatite and microtexture thereof and biology performance are relatively ", studied respectively and carried out agglomerating biological ceramics sample with traditional method and microwave method, the biological ceramics density that discovery microwave sintering method makes is big, grain-size obviously reduces, biocompatibility is good.
Above microwave sintering research is purpose to obtain fine and close hydroxyapatite all.Porous ceramics more can enlarge the Application of Biomaterial field in bioceramic material, and Y.Fang etc. are in " Fabrication of porous hydroxyapatite ceramics by microwaveprocessing " literary composition, with (the NH of difference amount
4)
2CO
3H
2O is a pore-forming material, makes base substrate just under the pressure of 140MPa, prepares the porous hydroxyapatite pottery with microwave sintering, at 1150～1200 ℃ of sintering 1～5min, has obtained the porous ceramics of porosity from 10% to 70%.But, this studies resulting porous ceramics grain-size is 280nm, do not reach nano-scale (＜100nm), and the pore dimension of gained sample also can not satisfy the required 100 μ m～400 μ m requirements of osseous tissue growth.
Microwave sintering is compared with normal sintering and has been demonstrated tangible advantage, but microwave sintering is hampered by such as problems such as focus, cracking, thermal runaway and non-uniform heating all the time, and the incubation cavity device complexity for preventing that the problems referred to above are provided with.
Three. summary of the invention
The objective of the invention is provides a kind of preparation method who prepares nano-biological cerimic at the deficiencies in the prior art, and it can not only improve the mechanical property and the biological activity of material, and device is simple, is easy to realize.
The object of the present invention is achieved like this:
The preparation method of nano-biological cerimic:
1. by the powdery pulp of the synthetic tool nanostructure of chemical process, after centrifugation, obtain containing the thick slurry of water 30～70%;
2. above-mentioned thick slurry is inserted dispersion agent, binding agent or rheological agent and the whipping agent of suitable proportion, the flowable slurry of furnishing places the baking oven moulding, and mold temperature is 30～120 ℃, obtain having the first base substrate of three-dimensional porous structure, get rid of organic binding through 300～800 ℃ again;
3. the biological ceramics base substrate is placed the dielectric material that is loaded in the microwave sintering container, sintering atmosphere is an air;
4. first base substrate is carried out microwave sintering, 800～1400 ℃ of sintering temperatures, 25～200 ℃/min of heat-up rate, soaking time 0.5～30min;
5. cooling rate is 50～200 ℃/min, and sample temperature to be sintered is reduced to the room temperature discharging.
Wherein, the nano-biological cerimic material comprises the mixture of titanium dioxide, alchlor, calcium phosphate series material and above material arbitrary proportion, and wherein the calcium phosphate series material is at least a in hydroxyapatite, tricalcium phosphate, tetracalcium phosphate, the Calcium Pyrophosphate; The microwave-assisted sintered medium is CaCO
3, CaO, MnO
2, Y
2O
3, Cr
2O
3, graphite, limestone, carbon dust, ZrO
2, Al
2O
3And/or at least a among the SiC.
The microwave sintering container that loads the microwave sintering medium is SiC or ZrO
2Sintering container, and should place the microwave sintering chamber.
The grain-size of products therefrom can reduce to 50nm-100nm from 1 μ m-2 μ m of normal sintering, and grain size is evenly distributed, and intercrystalline maintains micropore, thereby the mechanical strength of gained sample, biological activity all are better than the normal sintering under the corresponding conditions.
The present invention has the following advantages:
1. reduce the drying process of powder, shortened the technical process of pottery preparation greatly;
2. can effectively avoid problems such as focus, cracking, thermal runaway and non-uniform heating;
3. adopting air is sintering atmosphere, and agglomerating plant is simple and be easy to realize;
4. sintering temperature is low, speed is fast.Reduce by 100～200 ℃ than the normal sintering firing temperature, and the ceramic post sintering time only is 1/12～1/20 of normal sintering, and the grain-size of sintered product is less simultaneously, and grain size is evenly distributed, intercrystalline maintains micropore, thereby mechanical strength, biological activity are all better.
Four. description of drawings
Fig. 1 is the section SEM figure of the nanoporous hydroxylapatite ceramic sample of preparation
Left side figure amplifies 100 times SEM figure, and gained sample hole is of a size of 100～300 μ m as seen from the figure; Right figure amplifies 40000 times of SEM figure, and the average grain size of gained sample is 76nm, and maintains abundant microporous at intercrystalline.
Five. concrete embodiment
Below by example the present invention is specifically described.Be necessary to be pointed out that at this: present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1:
The 1.0M ca nitrate soln of measuring 160 milliliters is in 400 milliliters beaker, control reaction temperature is 60 ℃, and dropping ammonia transfers to 9.0 with the pH value, is not then stopping under the stirring, drip 100 milliliters of strong aqua and 1.0M ammonium dibasic phosphate solutions simultaneously, make the pH value maintain 9.0.After adding, stop and stirred 30 minutes, still aging 24 hours (the maintenance temperature of reaction is constant), eccentric cleaning to powder pH value is 7.0.This powder slip is added 10 milliliters in 5% hydrogen peroxide, polyoxyethylene glycol 1 gram, the flowable slurry of furnishing moves into mould and places the baking oven moulding, and mold temperature is 30～120 ℃.The demoulding also can obtain porous base substrate just through 400 ℃ of biscuitings.
The first base substrate of porous is placed within the SiC sintering container, and adopt SiC powder landfill, under air atmosphere, carry out microwave sintering as sintered medium.Heat-up rate is set at 40 ℃/min, treats to be incubated 5min after temperature rises to 1100 ℃, and cooling rate is set at 100 ℃/min, treat that sample is cooled to room temperature after, taking out the porosity that sample records sample is 65%, ultimate compression strength is 12MPa, grain-size 50-100nm.
Embodiment 2:
Get commodity nanometer level titanium dioxide powder 10 grams, add 10 gram water and be made into slurry, and in this slurry, add 5 milliliters in 5% hydrogen peroxide, polyvinyl alcohol 1 gram, the flowable slurry of furnishing moves into mould and places the baking oven moulding, and mold temperature is 30～120 ℃.The demoulding also can obtain porous base substrate just through 400 ℃ of biscuitings.
The first base substrate of porous is placed within the SiC sintering container, and adopt the powdered graphite landfill, under air atmosphere, carry out microwave sintering as sintered medium.Heat-up rate is set at 30 ℃/min, treats to be incubated 5min after temperature rises to 900 ℃, and cooling rate is set at 80 ℃/min, treat that sample is cooled to room temperature after, taking out the porosity that sample records sample is 60%, ultimate compression strength is 18MPa, grain-size 50-70nm.
Claims (2)
1. the preparation method of a nano porous biologic ceramics promptly adopts directly foam base technology and microwave sintering process of the synthetic slip of liquid phase to prepare the nanoporous pottery, it is characterized in that:
(1) by the synthetic powder slip with nanostructure of chemical process, the water content of slip is 30～70% after separating;
(2) the powder slip is through foaming, and mold temperature is 30～120 ℃, obtains having the first base substrate of three-dimensional porous structure, gets rid of organic binding through 300～800 ℃;
(3) the biological ceramics base substrate is placed the dielectric material that is loaded in the microwave sintering container, sintering atmosphere is an air;
(4) first base substrate is carried out microwave sintering, 800～1400 ℃ of sintering temperatures, 25～200 ℃/min of heat-up rate, soaking time 0.5～30min;
(5) cooling rate is 50～200 ℃/min, and sample temperature to be sintered is reduced to the room temperature discharging;
Wherein, the nano-biological cerimic material comprises the mixture of titanium dioxide, aluminium sesquioxide, calcium phosphate series material and above material arbitrary proportion, and wherein the calcium phosphate series material is at least a in hydroxyapatite, tricalcium phosphate, tetracalcium phosphate, the Calcium Pyrophosphate; The microwave-assisted sintered medium is CaCO
3, CaO, MnO
2, Y
2O
3, Cr
2O
3, graphite, limestone, carbon dust, ZrO
2, Al
2O
3And/or at least a among the SiC.
2. according to the described preparation method of claim 1, it is characterized in that the microwave sintering container is SiC or ZrO
2Sintering container, and should place the microwave sintering chamber.
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| CN100554216C (en) * | 2007-12-11 | 2009-10-28 | 北京科技大学 | A kind of method that adopts the microwave method synthesizing barium ferrocobalt niobium oxide material |
| CN101555159B (en) * | 2009-04-07 | 2012-05-23 | 同济大学 | Directional orifice carbide biological ceramic material and preparation method thereof |
| CN101786162B (en) * | 2010-01-19 | 2011-07-27 | 武汉科技大学 | Preparation method of bismuth telluride based bulk nano crystalline thermoelectric material |
| CN102543269A (en) * | 2012-01-20 | 2012-07-04 | 中国科学院上海硅酸盐研究所 | High-quality graphene transparent conductive film and production method thereof |
| CN104045365B (en) * | 2013-03-12 | 2016-08-17 | 珠海霍普金斯医药研究院股份有限公司 | A kind of method preparing calcium pyrophosphate crystal whisker toughened organizational project cancellous bony material |
| CN104496459B (en) * | 2014-12-02 | 2016-12-07 | 佛山铭乾科技有限公司 | A kind of Nano-grained Hydroxyapatite Ceramics and preparation method thereof |
| CN104803672A (en) * | 2015-03-31 | 2015-07-29 | 苏州维泰生物技术有限公司 | Calcium phosphate bioactive ceramic and preparation method thereof |
| CN104744021A (en) * | 2015-03-31 | 2015-07-01 | 苏州维泰生物技术有限公司 | Wear-resisting aluminum oxide ceramic and preparation method thereof |
| CN106495682A (en) * | 2015-03-31 | 2017-03-15 | 蒋超 | Biological activity is higher, the preparation method of bone repair replacement bioceramic |
| CN104829222A (en) * | 2015-03-31 | 2015-08-12 | 苏州维泰生物技术有限公司 | Aluminum phosphate calcium biological ceramic and preparation method thereof |
| CN104744028A (en) * | 2015-03-31 | 2015-07-01 | 苏州维泰生物技术有限公司 | Tricalcium phosphate/silicon carbide composite biological ceramic and preparation method thereof |
| CN105397090B (en) * | 2015-10-30 | 2018-01-12 | 昆明理工大学 | A kind of preparation method of porous nickel-titanium/hydroxyapatite composite material |
| CN106673693A (en) * | 2016-12-23 | 2017-05-17 | 江南大学 | Preparation method of novel bioceramic porous material |
| CN106986625B (en) * | 2017-03-17 | 2019-11-05 | 山东师范大学 | A kind of preparation method of graphene/hydroxyapatite composite ceramic material |
| CN108002840A (en) * | 2017-11-30 | 2018-05-08 | 明光市裕阳新材料有限公司 | A kind of biology implantation ceramic material and preparation method |
| CN108114316B (en) * | 2017-12-22 | 2021-07-02 | 奥精医疗科技股份有限公司 | Ceramic-based dental bone powder and preparation method thereof |
| CN108975941A (en) * | 2018-09-17 | 2018-12-11 | 淄博正邦知识产权企划有限公司 | A kind of alumina ceramic material and preparation method thereof with biocompatibility |
| TWI791260B (en) * | 2021-08-12 | 2023-02-01 | 行政院農業委員會 | Two-stage sintering method for preparing porous biphasic calcium phosphate ceramic from calcium-containing biological waste |
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