CN106083028A - Biocompatibility preferably, for the composite boilogical ceramic of bone defect healing - Google Patents

Biocompatibility preferably, for the composite boilogical ceramic of bone defect healing Download PDF

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CN106083028A
CN106083028A CN201610401418.2A CN201610401418A CN106083028A CN 106083028 A CN106083028 A CN 106083028A CN 201610401418 A CN201610401418 A CN 201610401418A CN 106083028 A CN106083028 A CN 106083028A
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temperature
apatite powder
hydroxyapatite
hydroxy apatite
nano zircite
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不公告发明人
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Chong Mengxia
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Chong Mengxia
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    • A—HUMAN NECESSITIES
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    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
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    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
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Abstract

The invention discloses a kind of biocompatibility preferable, composite boilogical ceramic for bone defect healing, including: prepare hydroxy apatite powder: prepare hydroxyapatite by hydro-thermal method, then drying and crushing is sieved, the mean diameter of hydroxy apatite powder is 10 50 μm, hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: with Zirconium tetrachloride. as raw material, controlling material temperature is 350 370 DEG C, it is passed through hydrogen and argon, the reative cell speed of rotation 30 60r/min, time 20 40min, question response terminates, it is cooled to room temperature take out；The hydroxy apatite powder being coated with nano zircite is carried out cold moudling；The thickness of described nano zircite clad is 100 300nm；Material after molding is carried out high-temperature calcination, and temperature is 1,000 1400 DEG C, pressure 1.5 2.5GPa, time 0.5 1h；After calcining, taking-up to be cooled.

Description

Biocompatibility preferably, for the composite boilogical ceramic of bone defect healing
Technical field
The invention belongs to biomedical materials field, particularly to a kind of hydroxyapatite/zirconium oxide composite boilogical ceramic And the preparation method of this bioceramic.
Background technology
Biomaterial is to repair body tissue, substitute and the material of the performances such as regeneration.Owing to rustless steel exists molten The problem that analysis, corrosion and fatigue problem, plastics existence and stability difference and intensity are low.Bioceramic material obtains broad development, tool There is the most wide prospect of the application.
Bioceramic material is divided into bio-inert ceramic materials and biological active ceramic material, zirconium oxide bioceramic to belong to Bio-inert ceramic materials, has excellent anti-wear performance and mechanical strength, is typically used as Dental Erosion or substitution material；Hydroxyl Apatite bioceramic belongs to bioactive ceramics, and the structure of hydroxyapatite is similar to biological bone, therefore, and the hydroxyl phosphorus of synthesis Lime stone bioceramic is commonly used for replacement or the repair materials of skeleton.
The mechanical strength of zirconium oxide bioceramic is good, and hardness is high, under heavy loading, easily damages body；Hydroxyl Apatite bioceramic has preferable biocompatibility, and has induction stimulating growth performance, and shortcoming is that mechanical strength is poor, The most wear-resisting, therefore, if combined by bi-material, to accomplish to have complementary advantages, the composite boilogical ceramic obtained will be provided with relatively Good prospect of the application.
Patent documentation " the hydroxyapatite-zirconium dioxide composite bioceramic material of Application No. 200510027284.4 And preparation method thereof " disclose a kind of hydroxyapatite/zirconium oxide composite boilogical ceramic and preparation method thereof, this technical scheme with Zirconium dioxide is matrix central core, and spreads the zirconium dioxide by different proportion mixing and hydroxyapatite the most separately below Mixing intermediate layer, the surface layer of outermost layer overlay pure ha, form a kind of gradient laminated composite structure；At steel In mould, dry pressing under pressure is 10～30MPa, then pressureless sintering under 1500～1600 DEG C of high temperature, so that it may obtain hydroxyl Apatite-zirconium dioxide composite bioceramic material.
It follows that this technical scheme provides hydroxyapatite/zirconium oxide composite bioceramic material to be by hydroxy-apatite Stone and zirconium dioxide are fabricated to layer structure, and after cold moudling, prepared by high temperature sintering.The compound bio material prepared Material, its mechanical performance increases than hydroxylapatite biology material, but the most undesirable, and the density of material is less, high temperature After solid phase, in the layer structure of formation, the contact of zirconium dioxide and hydroxyapatite is not tight, have impact on the toughness of material, Therefore, the performance of material gets involved between the two, does not reach preferably to promote.
Summary of the invention
Present invention solves the technical problem that: for above-mentioned deficiency, overcome the defect of prior art, it is an object of the invention to provide one Plant hydroxyapatite/zirconium oxide composite boilogical ceramic and preparation method thereof.
Technical scheme: a kind of hydroxyapatite/zirconium oxide composite boilogical ceramic, with hydroxy apatite powder be Matrix material, with nano zircite as covering material, at hydroxy apatite powder Surface coating nano zircite；
Wherein, the mean diameter of hydroxy apatite powder is 10-50 μm, and the thickness of nano zircite clad is 100-300nm；
Wherein, hydroxy apatite powder is prepared by precipitation method or hydro-thermal method.
As preferably, in described hydroxyapatite, the ratio of Ga and P is 1:1.67.
A kind of preparation method of hydroxyapatite/zirconium oxide composite boilogical ceramic, preparation process is as follows:
(1) hydroxy apatite powder is prepared: prepare hydroxyapatite by hydro-thermal method or precipitation method, then drying and crushing mistake Sieve；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: with four chlorinations Zirconium is raw material, controls material temperature and is 350-370 DEG C, is passed through hydrogen and argon, and the gas flow of hydrogen is 400-600ml/ Min, the gas flow of argon is 100-300ml/min, adjust reaction chamber temperature to 820-1300 DEG C, the reative cell speed of rotation 30-60r/min, time 20-40min, question response terminates, and is cooled to room temperature and takes out；
(3) hydroxy apatite powder being coated with nano zircite is carried out cold moudling；
(4) material after molding being carried out high-temperature calcination, temperature is 1000-1400 DEG C, pressure 1.5-2.5GPa, time 0.5- 1h；
(5) after calcining, taking-up to be cooled, i.e. obtain block hydroxyapatite/zirconium oxide composite boilogical ceramic.
As preferably, in step (2) chemical vapour deposition reaction, the temperature of reative cell is 918 DEG C.
As preferably, in step (2) chemical vapour deposition reaction, the gas flow of hydrogen is 450-550ml/min.
As preferably, in step (4), the temperature of high-temperature calcination is 1100-1250 DEG C, pressure 1.8-2.2GPa.
Beneficial effect: hydroxyapatite/zirconium oxide composite boilogical ceramic that the present invention provides, is to utilize chemical gaseous phase to deposit Method, at hydroxy apatite powder Surface coating one layer close column crystal formation nano zircite, then by the method for high temperature solid-state, Form composite bioceramic material.
In preparation process, prepare hydroxyapatite first with hydro-thermal method or precipitation method, the hydroxy-apatite obtained Stone purity is higher, and fineness is even more ideal, then desirable chemical vapour deposition, in the reaction, by controlling the flow of hydrogen with anti- Answer room temperature so that the nano zircite of formation presents the column crystal formation of uniformity, then High Temperature High Pressure Fast Sintering, obtains Composite bioceramic material.
Thus hydroxyapatite/zirconium oxide composite boilogical ceramic, combines hydroxyl apatite bioceramic and zirconium oxide is raw The advantage of thing pottery so that composite ceramics has higher mechanical strength and has preferable biocompatibility, can be as tooth Or the repairing of alveolus and filling, the reparation of Cranial defect, and bone tuberculosis can be treated as artificial bone core.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but Should be appreciated that these describe simply as to further illustrate the features and advantages of the present invention rather than to the claims in the present invention Limit.
Embodiment 1:
A kind of hydroxyapatite/zirconium oxide composite boilogical ceramic, with hydroxy apatite powder as matrix material, with nano zircite For covering material, at hydroxy apatite powder Surface coating nano zircite.
Preparing above-mentioned hydroxyapatite/zirconium oxide composite boilogical ceramic according to the preparation method that the present invention provides, step is such as Under:
(1) hydroxy apatite powder is prepared: by CaHPO4With CaCO3Dispensing is carried out by the ratio 6:4 of the amount of material；Then carry out wet Method ball milling, time 24h；The slurry that ball milling is good is poured in container, adds distilled water, be stirred in the case of 95 DEG C of constant temperature, After completion of the reaction, place precipitation and obtain the precipitation of hydroxyapatite thing of white, the most dried 200 mesh sieves；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: with four chlorinations Zirconium is raw material, and controlling material temperature is 355 DEG C, is passed through hydrogen and argon, and the gas flow of hydrogen is 450ml/min, argon Gas flow is 200ml/min, adjust reaction chamber temperature to 836 DEG C, reative cell speed of rotation 30r/min, time 30min, treat Reaction terminates, and is cooled to room temperature and takes out；Wherein, the thickness of nano zircite clad is 110nm；
(3) hydroxy apatite powder being coated with nano zircite is carried out cold moudling；
(4) material after molding being carried out high-temperature calcination, temperature is 1200 DEG C, pressure 2GPa, time 1h；
(5) after calcining, taking-up to be cooled, i.e. obtain block hydroxyapatite/zirconium oxide composite boilogical ceramic.
Block hydroxyapatite/zirconium oxide the composite boilogical ceramic obtained is carried out performance detection: density 3.84kg/m3； Comprcssive strength 620MPa；Bending strength 440MPa；Toughness 11MPa m1/2；Elastic modelling quantity 72GPa.
Embodiment 2:
A kind of hydroxyapatite/zirconium oxide composite boilogical ceramic, with hydroxy apatite powder as matrix material, with nano zircite For covering material, at hydroxy apatite powder Surface coating nano zircite.
Preparing above-mentioned hydroxyapatite/zirconium oxide composite boilogical ceramic according to the preparation method that the present invention provides, step is such as Under:
(1) hydroxy apatite powder is prepared: by CaHPO4With CaCO3Dispensing is carried out by the ratio 6:4 of the amount of material；Then carry out wet Method ball milling, time 24h；The slurry that ball milling is good is poured in container, adds distilled water, be stirred in the case of 95 DEG C of constant temperature, After completion of the reaction, place precipitation and obtain the precipitation of hydroxyapatite thing of white, the most dried 200 mesh sieves；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: with four chlorinations Zirconium is raw material, and controlling material temperature is 355 DEG C, is passed through hydrogen and argon, and the gas flow of hydrogen is 600ml/min, argon Gas flow is 300ml/min, adjust reaction chamber temperature to 1276 DEG C, reative cell speed of rotation 60r/min, time 30min, treat Reaction terminates, and is cooled to room temperature and takes out；Wherein, the thickness of nano zircite clad is 280nm；
(3) hydroxy apatite powder being coated with nano zircite is carried out cold moudling；
(4) material after molding being carried out high-temperature calcination, temperature is 1250 DEG C, pressure 2GPa, time 1h；
(5) after calcining, taking-up to be cooled, i.e. obtain block hydroxyapatite/zirconium oxide composite boilogical ceramic.
Block hydroxyapatite/zirconium oxide the composite boilogical ceramic obtained is carried out performance detection: density 4.16kg/m3； Comprcssive strength 660MPa；Bending strength 470MPa；Toughness 12.5MPa m1/2；Elastic modelling quantity 77GPa.
Embodiment 3:
A kind of hydroxyapatite/zirconium oxide composite boilogical ceramic, with hydroxy apatite powder as matrix material, with nano zircite For covering material, at hydroxy apatite powder Surface coating nano zircite.
Preparing above-mentioned hydroxyapatite/zirconium oxide composite boilogical ceramic according to the preparation method that the present invention provides, step is such as Under:
(1) hydroxy apatite powder is prepared: by CaHPO4With CaCO3Dispensing is carried out by the ratio 6:4 of the amount of material；Then carry out wet Method ball milling, time 24h；The slurry that ball milling is good is poured in container, adds distilled water, be stirred in the case of 95 DEG C of constant temperature, After completion of the reaction, place precipitation and obtain the precipitation of hydroxyapatite thing of white, the most dried 200 mesh sieves；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: with four chlorinations Zirconium is raw material, and controlling material temperature is 355 DEG C, is passed through hydrogen and argon, and the gas flow of hydrogen is 500ml/min, argon Gas flow is 200ml/min, adjust reaction chamber temperature to 918 DEG C, reative cell speed of rotation 45r/min, time 35min, treat Reaction terminates, and is cooled to room temperature and takes out；Wherein, the thickness of nano zircite clad is 210nm；
(3) hydroxy apatite powder being coated with nano zircite is carried out cold moudling；
(4) material after molding being carried out high-temperature calcination, temperature is 1200 DEG C, pressure 2GPa, time h；
(5) after calcining, taking-up to be cooled, i.e. obtain block hydroxyapatite/zirconium oxide composite boilogical ceramic.
Block hydroxyapatite/zirconium oxide the composite boilogical ceramic obtained is carried out performance detection: density 4.05kg/m3； Comprcssive strength 650MPa；Bending strength 450MPa；Toughness 11.5MPa m1/2；Elastic modelling quantity 72GPa.
Embodiment 4:
A kind of hydroxyapatite/zirconium oxide composite boilogical ceramic, with hydroxy apatite powder as matrix material, with nano zircite For covering material, at hydroxy apatite powder Surface coating nano zircite.
Preparing above-mentioned hydroxyapatite/zirconium oxide composite boilogical ceramic according to the preparation method that the present invention provides, step is such as Under:
(1) hydroxy apatite powder is prepared: by this method Ca (NO3)2With (NH4)2HPO4React, obtain the hydroxyl of white Apatite precipitates, the most dried 200 mesh sieves；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: with four chlorinations Zirconium is raw material, and controlling material temperature is 360 DEG C, is passed through hydrogen and argon, and the gas flow of hydrogen is 500ml/min, argon Gas flow is 250ml/min, adjust reaction chamber temperature to 918 DEG C, reative cell speed of rotation 60r/min, time 40min, treat Reaction terminates, and is cooled to room temperature and takes out；Wherein, the thickness of nano zircite clad is 230nm；
(3) hydroxy apatite powder being coated with nano zircite is carried out cold moudling；
(4) material after molding being carried out high-temperature calcination, temperature is 1250 DEG C, pressure 2.5GPa, time 0.5h；
(5) after calcining, taking-up to be cooled, i.e. obtain block hydroxyapatite/zirconium oxide composite boilogical ceramic.
Block hydroxyapatite/zirconium oxide the composite boilogical ceramic obtained is carried out performance detection: density 4.12kg/m3； Comprcssive strength 660MPa；Bending strength 460MPa；Toughness 12MPa m1/2；Elastic modelling quantity 74GPa.
Embodiment 5:
A kind of hydroxyapatite/zirconium oxide composite boilogical ceramic, with hydroxy apatite powder as matrix material, with nano zircite For covering material, at hydroxy apatite powder Surface coating nano zircite.
Preparing above-mentioned hydroxyapatite/zirconium oxide composite boilogical ceramic according to the preparation method that the present invention provides, step is such as Under:
(1) hydroxy apatite powder is prepared: by this method Ca (NO3)2With (NH4)2HPO4React, obtain the hydroxyl of white Apatite precipitates, the most dried 200 mesh sieves；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: with four chlorinations Zirconium is raw material, and controlling material temperature is 365 DEG C, is passed through hydrogen and argon, and the gas flow of hydrogen is 550ml/min, argon Gas flow is 300ml/min, adjust reaction chamber temperature to 918 DEG C, reative cell speed of rotation 60r/min, time 30min, treat Reaction terminates, and is cooled to room temperature and takes out；
Wherein, the thickness of nano zircite clad is 200nm；
(3) hydroxy apatite powder being coated with nano zircite is carried out cold moudling；
(4) material after molding being carried out high-temperature calcination, temperature is 1200 DEG C, pressure 2GPa, time 1h；
(5) after calcining, taking-up to be cooled, i.e. obtain block hydroxyapatite/zirconium oxide composite boilogical ceramic.
Block hydroxyapatite/zirconium oxide the composite boilogical ceramic obtained is carried out performance detection: density 3.96kg/m3； Comprcssive strength 630MPa；Bending strength 470MPa；Toughness 12MPa m1/2；Elastic modelling quantity 75GPa.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention. Multiple amendment to these embodiments will be apparent from for those skilled in the art, as defined herein General Principle can realize without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention It is not intended to be limited to the embodiments shown herein, and is to fit to and principles disclosed herein and features of novelty phase one The widest scope caused.

Claims (1)

1. the preparation method of hydroxyapatite/zirconium oxide composite boilogical ceramic, it is characterised in that preparation process is as follows:
(1) hydroxy apatite powder is prepared: preparing hydroxyapatite by precipitation method, then drying and crushing is sieved, hydroxyl The mean diameter of apatite powder is 10-50 μm, and in hydroxyapatite, the ratio of Ga and P is 1:1.67；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: with four chlorinations Zirconium is raw material, controls material temperature and is 350-370 DEG C, is passed through hydrogen and argon, and the gas flow of hydrogen is 450-550ml/ Min, the gas flow of argon is 100-300ml/min, adjust reaction chamber temperature to 820-1300 DEG C, the reative cell speed of rotation 30-60r/min, time 20-40min, question response terminates, and is cooled to room temperature and takes out；
(3) hydroxy apatite powder being coated with nano zircite is carried out cold moudling；Described nano zircite clad Thickness is 100-300nm；
(4) material after molding being carried out high-temperature calcination, temperature is 1100-1250 DEG C, pressure 1.8-2.2GPa, time 0.5- 1h；
(5) after calcining, taking-up to be cooled, i.e. obtain block hydroxyapatite/zirconium oxide composite boilogical ceramic.
CN201610401418.2A 2014-11-10 2014-11-10 Biocompatibility preferably, for the composite boilogical ceramic of bone defect healing Withdrawn CN106083028A (en)

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