CN108395237A - A kind of high intensity silicon calcium phosphate biological ceramic material and preparation method thereof - Google Patents
A kind of high intensity silicon calcium phosphate biological ceramic material and preparation method thereof Download PDFInfo
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- CN108395237A CN108395237A CN201810175886.1A CN201810175886A CN108395237A CN 108395237 A CN108395237 A CN 108395237A CN 201810175886 A CN201810175886 A CN 201810175886A CN 108395237 A CN108395237 A CN 108395237A
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Abstract
The present invention relates to a kind of high intensity silicon calcium phosphate biological ceramic materials and preparation method thereof.The method includes the steps：(1) Zinc oxide powder, silicon calcium phosphate powder and binder are uniformly mixed, obtain mixture, then the mixture is molded, obtains ceramic body；(2) ceramic body that step (1) obtains is sintered, high intensity silicon calcium phosphate biological ceramic material is made.The method of the present invention has the advantages that simple for process, technique is controllable, easy to operate and sintering temperature is low etc.；High intensity silicon calcium phosphate biological ceramic material produced by the present invention has many advantages, such as that the porosity low (porosity can be reduced to 1% or so), bending strength high (bending strength can be improved to 65~90MPa) and cell compatibility are good, it is particularly suitable for being used as hard tissue repairing material, it is a kind of biology and medical material for having very much a potentiality, may be used as the reparation, filling and materials of bone tissue of bone tissue.
Description
Technical field
The invention belongs to the preparation field of bioceramic more particularly to a kind of high intensity silicon calcium phosphate biological ceramic material and
Preparation method.
Background technology
With the extension of human longevity, by wound, incidence of fracture caused by old bone is crisp or disease expect the year two thousand fifty
400% can be risen to, the thing followed is huge medical consumption, it is estimated that, the annual incidence in the whole world/death rate is spent
About 8,000,000,000 dollars will accordingly be increased, service charge about increases 800,000 dollars, it can be seen that bone renovating material is in worldwide
Market potential it is huge.From the point of view of national situations, China is a big country for possessing ten thousand disabled persons more than 1,300,000,000 populations and 8000, according to
The civil affairs department reports, by the end of 2005, limbs not free patient in China's was more than 15,000,000, wherein deformed limb person about 8,000,000, by
The patients with Kashin-Beck Disease that rheumatoid causes has millions of；And the data of the 6th national census are shown, China is just stepping into always
Year, people was social, and 60 years old or more elderly population account for about the 13.26% of national population up to 1.78 hundred million.It is repaiied as it can be seen that carrying out bone tissue
Research in terms of multiple material has great social effect and economic benefit.
With the development of material science, in recent decades, artificial synthesized Bone Defect Repari has become various countries' research with alternative materials
The hot spot of exploitation is one of the important content of bio-medical material research.Currently, inorganic material is still Bone Defect Repari and replacement material
The first choice of material, research are also the most extensive.It is the calcium phosphate similar with human body inorganic constituents clinically to obtain at present widely applied
Class bioceramic, calcium phosphate bioceramic are nontoxic to human body, harmless, without carcinogenic work due to good biocompatibility
With, but it lacks bioactivity, while degradability performance is also not ideal enough.
Professor Hench at the beginning of the seventies in last century, the U.S. has found that silicon has the function of induced osteogenesis, to siliceous biology
Active material has obtained extensive research.Our early-stage study finds silicon calcium phosphate (Ca5(PO4)2SiO4, CPS) material have with
The similar crystal structure of hydroxyapatite, silicon components therein can induce the generation of osteoid apatite, to promote the shape of new bone
At；The degradation of calcium and phosphorus component can provide calcium and phosphorus for the growth of new bone simultaneously, to accelerate osteanagenesis process.
Silicon calcium phosphate as a kind of biomaterial newly developed, be all also absorbed in the world at present in preparation method and its
In the exploratory development of biological property, the research work of early period shows that current preparation method hardly results in mechanical property and biology
The all good material system of activity.Therefore how to optimize the sintering character of silicon calcium phosphate ceramic, realize high mechanical property and good
The perfect adaptation of biology performance is that silicon calcium phosphate goes further to the clinical critical issue that must be solved.
Invention content
In order to solve one or more technical problem, the object of the present invention is to provide a kind of high intensity silicon calcium phosphate biologies
Ceramic material and preparation method thereof.It is excellent that the method for the present invention has that simple for process, technique is controllable, easy to operate and sintering temperature is low etc.
Point, high intensity silicon calcium phosphate biological ceramic material prepared by the method for the present invention is low with the porosity, bending strength is high and cell
The advantages that compatibility is good.
The present invention provides a kind of preparation method of high intensity silicon calcium phosphate biological ceramic material, the side in first aspect
Method includes the following steps：
(1) Zinc oxide powder, silicon calcium phosphate powder and binder are uniformly mixed, obtain mixture, it then will be described mixed
It closes material to be molded, obtains ceramic body；With
(2) ceramic body that step (1) obtains is sintered, high intensity silicon calcium phosphate biological ceramic material is made.
Preferably, the mass ratio of the Zinc oxide powder and the silicon calcium phosphate powder is (0.1~5)：(95~99.9),
Preferably (0.5~5)：(95~99.5).
Preferably, the sintering includes the sintering of the first temperature stage and the sintering of second temperature stage；The first temperature rank
The temperature of section sintering is 500 DEG C~700 DEG C, and the time of the first temperature stage sintering is 30~120min；Second temperature
Spend the stage sintering temperature be 800 DEG C~1400 DEG C, preferably 1100 DEG C~1400 DEG C, more preferably 1250 DEG C~1350 DEG C,
The time of the second temperature stage sintering is 30~360min, preferably 60~240min.
Preferably, the temperature of sintering is risen to using the heating rate of 1 DEG C/min~10 DEG C/min in step (2).
Preferably, the dosage of the binder accounts for the sum of the Zinc oxide powder and the silicon calcium phosphate powder dosage
0.1~5wt%, preferably 0.1~2wt%.
Preferably, the binder is water based adhesive.
Preferably, uniform by ball milling mixing using water as ball-milling medium in step (1).
Preferably, in step (1), the mixture is subjected to dry-pressing formed and cold isostatic compaction successively.
Particularly, the dry-pressing formed pressure is 5~100MPa, preferably 10~50MPa, the dry-pressing formed guarantor
The pressure time is 1~10min, preferably 2~8min；And/or the pressure of the cold isostatic compaction is 50~400MPa, preferably
The dwell time of 100~300MPa, the cold isostatic compaction are 1~10min, preferably 2~8min.
The present invention provides high intensity silicon phosphorus made from preparation method of the present invention described in first aspect in second aspect
Sour calcium bioceramic material；Preferably, the bending strength of the high intensity silicon calcium phosphate biological ceramic material is not less than
65MPa, the porosity are less than 5%.
The present invention at least has the advantages that compared with prior art：
(1) present invention is added a small amount of zinc oxide and is prepared with silicon phosphorus as sintering aid based on silicon calcium phosphate powder
Sour calcium is main phase, also has the existing high intensity silicon calcium phosphate biological ceramic material containing zinc of zinc oxide and third phase hardystonite
Material；High intensity silicon calcium phosphate biological ceramic material prepared by the method for the present invention has and causes compared with pure silicon calcium phosphate biological ceramic
Close microstructure significantly improves the sintering character and mechanical property of silicon calcium phosphate biological ceramic material, in addition, with more excellent
Different biological property, the high intensity silicon calcium phosphate biological ceramic material because the presence of zinc makes it possess better osteogenic activity,
And there is certain inhibiting effect to osteoclast, be conducive to the bioactivity and the degradation that improve silicon calcium phosphate biological ceramic material
Performance.
(2) present invention is compared with present technology, using zinc oxide as sintering aid, by liquid-phase sintering, reduces sintering temperature
Degree (sintering temperature be reduced to 1300 DEG C even lower), the high intensity silicon calcium phosphate biological ceramic material sintering temperature being prepared
The low, porosity (porosity) is low, mechanical property is good and biology performance is good；The method of the present invention is overcoming conventional atmospheric agglomerant
It on the basis of skill defect, solves the problems, such as silicon calcium phosphate biological ceramic hard-to-sinter, poor mechanical property, is that one kind is suitable for advising greatly
The method that mould prepares strong mechanical performance silicon calcium phosphate biological ceramic material.
(3) the method for the present invention has the advantages that simple for process, technique is controllable, easy to operate and sintering temperature is low etc.；The present invention
High intensity silicon calcium phosphate biological ceramic material made from method has the porosity low (porosity can be reduced to 1% or so), bending resistance
The advantages that intensity height (bending strength can be improved to 65~90MPa) and good cell compatibility, is particularly suitable for being used as sclerous tissues
Repair materials are a kind of biologies and medical material for having very much a potentiality, such as can be used for the reparation, filling and gear division of bone tissue
Repair materials etc..
Description of the drawings
Fig. 1 is the cross-section morphology figure of high intensity silicon calcium phosphate biological ceramic material prepared by embodiment 1.
Fig. 2 is the cross-section morphology figure of high intensity silicon calcium phosphate biological ceramic material prepared by embodiment 2.
Fig. 3 is the cross-section morphology figure of high intensity silicon calcium phosphate biological ceramic material prepared by embodiment 3.
Fig. 4 is the cross-section morphology figure of high intensity silicon calcium phosphate biological ceramic material prepared by embodiment 4.
Fig. 5 is the cross-section morphology figure of high intensity silicon calcium phosphate biological ceramic material prepared by embodiment 5.
Fig. 6 is the cross-section morphology figure of high intensity silicon calcium phosphate biological ceramic material prepared by embodiment 6.
Fig. 7 is the cross-section morphology figure of silicon calcium phosphate biological ceramic material prepared by comparative example 1.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiment of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of the every other embodiment that is obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of high intensity silicon calcium phosphate biological ceramic material, the side in first aspect
Method includes the following steps：
(1) Zinc oxide powder, silicon calcium phosphate powder and binder are uniformly mixed, obtain mixture, it then will be described mixed
It closes material to be molded, obtains ceramic body；With
(2) ceramic body that step (1) obtains is sintered (normal pressure-sintered), high intensity silicon calcium phosphate biology pottery is made
Ceramic material.
In the present invention, using normal pressure-sintered technique, this is simple for process controllable, the zinc oxide for using bio-safety nontoxic for
Sintering aid, silicon calcium phosphate be main phase, be added binder, by evenly mixing, molding after carry out it is normal pressure-sintered be prepared it is high-strength
Spend silicon calcium phosphate biological ceramic material；The present invention reduces sintering for sintering aid by using zinc oxide by low-temperature eutectic
Temperature forms liquid phase (liquid-phase sintering) between ceramic particle, promotes the densification of ceramic particle in sintering range, this
Outside, zinc oxide can also significantly improve the mechanical property of silicon calcium phosphate biological ceramic material, to prepare the porosity (hole
Rate) low, excellent in mechanical performance, and the high intensity silicon calcium phosphate biological ceramic material that biology performance further increases.The present invention
The high intensity silicon calcium phosphate biological ceramic material of preparation has zinc oxide and third phase hardystonite using silicon calcium phosphate as main phase, also
Presence.
In the present invention, the Zinc oxide powder is selected from by six side's Zinc oxide powders, cubic oxide zinc powder body and octahedral oxygen
The group of change zinc powder body composition, preferably six side's Zinc oxide powders, because six side's zinc oxide stability highests, are easiest to obtain, because
And it is cheap, reduce the cost of raw material.
In the present invention, the silicon calcium phosphate powder can for example pass through sol-gel method, solid reaction process, hydro-thermal method
Or other methods are prepared；Preferably, the silicon calcium phosphate powder is prepared by sol-gel method.Silicon calcium phosphate
Powder can be prepared voluntarily, and preparation method for example can be：
(a) by ethyl orthosilicate 22.4 milliliters mixed with 4 milliliters of the nitric acid of a concentration of 2 mol/L, and be added 9.6 milliliters
Deionized water and 5.8 milliliters of absolute ethyl alcohols, are stirred at room temperature 2 hours, are subsequently added into 34.2 milliliters of triethyl phosphates, continue to stir
It mixes 2 hours, 118.1 grams of calcium nitrate tetrahydrate is then added, stir 4 hours, obtain silicon Calcium phosphate gel；By colloidal sol at 60 DEG C
Ageing 48 hours, obtains gel；Gel is 120 hours dry at 120 DEG C, obtain xerogel.
(b) xerogel is ground into powder, is preferably to calcine 1~10 at 1100 DEG C~1400 DEG C at 1000 DEG C~1600 DEG C
Hour, it preferably calcines 2~6 hours, such as calcine 6 hours (2 DEG C/min of heating rate) at 1400 DEG C, silicon calcium phosphate is made
(Ca5(PO4)2SiO4, CPS) and powder.
According to some preferred embodiments, the mass ratio of the Zinc oxide powder and the silicon calcium phosphate powder is (0.1
~5)：(95~99.9), preferably (0.5~5)：(95~99.5).In the present invention, by Zinc oxide powder and silicon phosphoric acid calcium powder
The quality sum of body is denoted as powder gross mass, i.e., the described Zinc oxide powder accounts for 0.1~5wt% of powder gross mass, preferably 0.5
~5wt% (such as 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%,
4.5wt% or 5.0wt%), the silicon calcium phosphate powder accounts for 95~99.9wt% of powder gross mass, preferably 95~
99.5wt%.In the present invention, the mass percent that Zinc oxide powder is accounted for powder gross mass is denoted as the additive amount of zinc oxide.
In the present invention, it is preferred to account for 0.5~5wt% of powder gross mass for the Zinc oxide powder, and 0.5~
In the range of 5wt%, the mass percent shared by Zinc oxide powder is moderate preferably, continues to increase with Zinc oxide powder additive amount
Add, the amount of liquid phase of the Zinc oxide powder generated in sintering process is reduced instead, high intensity silicon calcium phosphate biological ceramic obtained
The porosity not anti-reflection of material increases, and additionally reduces bending strength.Therefore moderate zinc oxide content advantageously forms enough
Liquid phase, may advantageously facilitate crystal grain and grow up to be moved out stomata.
According to some preferred embodiments, the sintering can be carried out directly under a sintering temperature, the sintering
Temperature be 500 DEG C~1400 DEG C (such as 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C,
1300 DEG C or 1400 DEG C), preferably 1100 DEG C~1400 DEG C (such as 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C,
1350 DEG C or 1400 DEG C), more preferably 1250 DEG C~1350 DEG C (such as 1250 DEG C, 1300 DEG C or 1350 DEG C)；The sintering
Time is 30~360min (such as 30,60,90,120,150,180,210,240,270,300,330 or 360min), preferably
60~240min (such as 60,90,120,150,180,210 or 240min).Within the temperature range of 1100 DEG C~1400 DEG C, oxygen
Changing zinc can play one's part to the full as sintering aid, can be fully sintered between ceramic particle and crystallite dimension will not be because
It is excessively high and excessive for temperature, it will not be melted because liquid content is excessively high；In addition, sintering temperatures different in the present invention
The bending strength and the trepanning porosity of high intensity silicon calcium phosphate biological ceramic material can be had an impact.
According to some preferred embodiments, the sintering includes burning in the sintering of the first temperature stage and second temperature stage
Knot；The temperature of first temperature stage sintering is 500 DEG C~700 DEG C (such as 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C or 700
DEG C), the time of the first temperature stage sintering is 30~120min (such as 30,60,90 or 120min)；The second temperature
Stage sintering temperature be 800 DEG C~1400 DEG C (such as 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C, 1300 DEG C or
1400 DEG C), preferably 1100 DEG C~1400 DEG C (such as 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C, 1350 DEG C or
1400 DEG C), more preferably 1250 DEG C~1350 DEG C (such as 1250 DEG C, 1300 DEG C or 1350 DEG C), the second temperature stage burns
The time of knot is 30~360min (such as 30,60,90,120,150,180,210,240,270,300,330 or 360min), excellent
It is selected as 60~240min (such as 60,90,120,150,180,210 or 240min).In the present invention, it is preferred to for first by ceramic blank
The sintering (sintering of the first temperature stage) of body one relative low temperature of progress carries out sintering (the second temperature stage burning of relatively-high temperature again
Knot), it has been surprisingly found that the porosity that can effectively reduce high intensity silicon calcium phosphate biological ceramic material obtained and to improve it anti-
Curved intensity, the possible reason is, organic matter (binder) can be effectively removed in the sintering of the first temperature stage, avoided
Sintering character and mechanical property etc. of the organic matter in the sintering of relatively-high temperature to high intensity silicon calcium phosphate biological ceramic material
Influence.
According to some preferred embodiments, in step (2) using 1 DEG C/min~10 DEG C/min (such as 1,2,3,4,
5,6,7,8,9 or 10 DEG C/min) heating rate rise to the temperature of sintering.In the present invention, using relatively slow heating speed
Rate (1 DEG C/min~10 DEG C/min) rises to required sintering temperature, advantageously forms uniform texture and the high height of compactness
Intensity silicon calcium phosphate biological ceramic material.
According to some preferred embodiments, the dosage of the binder accounts for the Zinc oxide powder and the silicon calcium phosphate
The sum of powder dosage 0.1~5wt% (such as 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 1.0wt%,
1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt% or 5.0wt%), preferably 0.1~
2wt% (such as 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%,
0.9wt%, 1.0wt%, 1.2wt%, 1.5wt%, 1.8wt% or 2.0wt%).
In the present invention, the binder is, for example, organic binder, and the binder is preferably water based adhesive.At this
In invention, the binder can be added as a solution, such as when the water based adhesive is polyvinyl alcohol, Ke Yipei
Be made polyvinyl alcohol water solution addition, the concentration of the polyvinyl alcohol water solution be preferably 1~10wt% (such as 1wt%,
2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%).Particularly, in the present invention, it removes
Except polyvinyl alcohol, the water based adhesives such as polyethylene glycol or starch can also be used.
According to some preferred embodiments, in step (1), using water as ball-milling medium, by ball milling (for example, by using row
Celestial body grinding machine) it is uniformly mixed.In the present invention, planetary ball mill will be used to carry out ball milling and is denoted as planetary ball mill.
According to some preferred embodiments, in step (1), the mixture is carried out successively dry-pressing formed and cold etc.
Hydrostatic profile；The dry-pressing formed pressure be 5~100MPa, preferably 10~50MPa (such as 10,20,30,40 or
50MPa), the dry-pressing formed dwell time is 1~10min, preferably 2~8min (such as 2,3,4,5,6,7 or 8min)；
And/or the pressure of the cold isostatic compaction is 50~400MPa, preferably 100~300MPa (such as 100,150,200,250
Or 300MPa), dwell time of the cold isostatic compaction is 1~10min, preferably 2~8min (such as 2,3,4,5,6,7
Or 8min).In the present invention, the mixture is subjected to dry-pressing formed and cold isostatic compaction successively, is conducive to be had
The ceramic body of some strength, to be also beneficial to obtain the height that uniform texture, densification degree are high and bending strength is high
Intensity silicon calcium phosphate biological ceramic material.It illustrates, being also using other forming method moldings in the present invention can
With.
According to some, more specifically embodiment, step (1) are：Six side's Zinc oxide powders and silicon phosphoric acid are weighed according to the ratio
Organic binder (polyvinyl alcohol water solution) is added using water as ball-milling medium in calcium powder body, and carrying out ball milling using planetary ball mill makes
It obtains each raw material to be uniformly mixed, obtains the mixture of finely dispersed six sides zinc oxide and silicon calcium phosphate powder, it then will be described mixed
It closes material and carries out drying and processing (50 DEG C~80 DEG C of drying temperature), after carrying out drying and processing, the mixture can also be sieved,
Obtain the mixture of uniform particle sizes, wherein gross mass and the ball milling of the six sides Zinc oxide powder with silicon calcium phosphate powder
The mass ratio (1~3) of the dosage of medium：(2~6), the Ball-milling Time can be 2~12 hours；Then by the mixture according to
The dry-pressing formed and cold isostatic compaction of secondary progress, obtains ceramic body.
According to some, more specifically embodiment, step (2) are：Ceramic body after molding progress is normal pressure-sintered,
Can be warming up to 500 DEG C with the heating rate of 1~10 DEG C/min, 0.5h~2h is with organics removal for heat preservation, then with 1~10
DEG C/heating rate of min is warming up to 800~1400 DEG C of final sintering temperature, soaking time is 30 minutes~6 hours, is cooled down
Journey is furnace cooling.
The present invention provides high intensity silicon phosphorus made from preparation method of the present invention described in first aspect in second aspect
Sour calcium bioceramic material；Preferably, the bending strength of the high intensity silicon calcium phosphate biological ceramic material is not less than
65MPa, the porosity are less than 5%.In the present invention, the porosity is also denoted as to the trepanning porosity or porosity.
Embodiment 1
Six side's Zinc oxide powders of 0.5g and 49.5g silicon calcium phosphate powders are weighed first, 50g deionized waters are added, and are added
5.0g solution concentrations are the polyvinyl alcohol water solution of 10wt%, and evenly dispersed mixture is made, then 60 in planetary ball mill 3h
12 hours dry at DEG C, sieving obtains the mixture of uniform particle sizes；Obtained mixture is subjected to dry-pressing (dry-pressing successively again
Briquetting pressure 50MPa, dwell time 5min) and cold isostatic compaction (the pressure 200MPa of cold isostatic compaction, dwell time
5min) processing obtains the strip that length is 3 × 4 × 40mm；Finally, strip is placed in alumina crucible and covers carry out normal pressure
Sintering is warming up to 500 DEG C with 2 DEG C/min heating rates and keeps the temperature 2 hours to remove no-bonder, then with 2 DEG C/min heating rates
It is warming up to 1300 DEG C (final sintering temperature) and keeps the temperature 2 hours, obtain the high intensity silicon calcium phosphate that oxidation Zinc supplementation is 1wt%
Bioceramic material.
High intensity silicon calcium phosphate biological ceramic material obtained by the present embodiment uses scanning electron microscope (SEM, S-
3400N TypeI, HITACHI, Japan) cross-section morphology observed is as shown in Figure 1；High intensity silicon obtained by the present embodiment
The physical property of calcium phosphate biological ceramic material and mechanical property are as shown in table 1, and wherein bending strength uses three-point bending method
(Instron-5566, Instron Co.Ltd., USA) is tested；Sintering shrinkage is using the front and back ceramics sample size of measurement sintering
Variation is calculated；The trepanning porosity is tested using Archimedes's drainage (national standard GB-T1966-1996).
Complex chart 1 and table 1 be not as can be seen that in contrast to six side's zinc oxide (comparative example 1) are added, made from the present embodiment
There is hardystonite in high intensity silicon calcium phosphate biological ceramic material, bending strength significantly improves, and the trepanning porosity is substantially reduced.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that：
The dosage of six side's Zinc oxide powders is 1.5g, and the dosage of silicon calcium phosphate powder is 48.5g, and oxidation Zinc supplementation is made
For the high intensity silicon calcium phosphate biological ceramic material of 3wt%；Other differences are as shown in table 1.
The cross-section morphology of high intensity silicon calcium phosphate biological ceramic material obtained by the present embodiment is as shown in Figure 2.Complex chart 2
And table 1 can be seen that the increase with oxidation Zinc supplementation, the densification degree of high intensity silicon calcium phosphate biological ceramic material
It improves, hardystonite content and remaining zinc oxide content increase.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that：
The dosage of six side's Zinc oxide powders is 2.5g, and the dosage of silicon calcium phosphate powder is 47.5g, and oxidation Zinc supplementation is made
For the high intensity silicon calcium phosphate biological ceramic material of 5wt%；Other differences are as shown in table 1.
The cross-section morphology of high intensity silicon calcium phosphate biological ceramic material obtained by the present embodiment is as shown in Figure 3.Complex chart 3
And table 1 is as can be seen that further increasing with oxidation Zinc supplementation, the trepanning of high intensity silicon calcium phosphate biological ceramic material
The porosity reduces amplitude and becomes smaller, and remaining zinc oxide content increases.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that：
Final sintering temperature is 1340 DEG C；Other differences are as shown in table 1.
The cross-section morphology of high intensity silicon calcium phosphate biological ceramic material obtained by the present embodiment is as shown in Figure 4.Complex chart 4
And table 1 is as can be seen that with the raising of final sintering temperature and the addition of zinc oxide, high intensity silicon calcium phosphate biological ceramic material
The densification degree of material further increases.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 2, the difference is that：Final sintering temperature is 1340 DEG C；Other differences
Place is as shown in table 1.
The cross-section morphology of high intensity silicon calcium phosphate biological ceramic material obtained by the present embodiment is as shown in Figure 5.Complex chart 5
And table 1 can be seen that the raising with final sintering temperature and aoxidize the increase of Zinc supplementation, high intensity silicon calcium phosphate biology
The densification degree of ceramic material further increases, and hardystonite content increases.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 3, the difference is that：Final sintering temperature is 1340 DEG C；Other differences
Place is as shown in table 1.
The cross-section morphology of high intensity silicon calcium phosphate biological ceramic material obtained by the present embodiment is as shown in Figure 6.Complex chart 6
And table 1 can be seen that with the raising of final sintering temperature and further increasing for oxidation Zinc supplementation, high intensity silicon phosphoric acid
The densification degree of calcium bioceramic material further increases, and hardystonite content increases.
Embodiment 7
Embodiment 7 is substantially the same manner as Example 1, the difference is that：
By strip be placed in alumina crucible cover carry out it is normal pressure-sintered, be directly warming up to the heating rate of 2 DEG C/min
1300 DEG C (final sintering temperature) keeps the temperature 4 hours, obtains the high intensity silicon calcium phosphate biology that oxidation Zinc supplementation is 1wt% and makes pottery
Ceramic material；Other differences are as shown in table 1.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, the difference is that：
Six side's Zinc oxide powders it are not mixed in mixture, i.e. the additive amount of zinc oxide is 0wt%.
The bending strength of silicon calcium phosphate biological ceramic material obtained by this comparative example is 40.9MPa, and the trepanning porosity is
22.6%, cross-section morphology figure is as shown in Figure 7.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, the difference is that：
Six side's Zinc oxide powders are replaced with hexagonal boron nitride powder；Other differences are as shown in table 1.
Table 1：The physical property and mechanical property of Examples 1 to 7 and comparative example 1~2.
The experimental results showed that：The three-point bending resistance intensity of high intensity silicon calcium phosphate biological ceramic material prepared by the present invention is not
Less than 65MPa, the trepanning porosity can be less than 5%.Zinc oxide is not added with as sintering aid compared to what is prepared under similarity condition
Silicon calcium phosphate biological ceramic material, the porosity is decreased obviously, and bending strength significantly improves.The present invention is by being added zinc oxide
(preferably six side's zinc oxide) are that sintering aid solves hard-to-sinter under silicon calcium phosphate biological ceramic material normal pressure, poor mechanical property
Problem.Preparation method in the present invention has the characteristics that preparation process is simple, technique is controllable, at low cost, can significantly extend silicon phosphorus
Application of the sour calcium bioceramic material in terms of bone substitutes bioceramic.Therefore, the high intensity silicon calcium phosphate prepared by the present invention
Bioceramic material can be applied to technical field of biological material.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of high intensity silicon calcium phosphate biological ceramic material, which is characterized in that the method includes walking as follows
Suddenly：
(1) Zinc oxide powder, silicon calcium phosphate powder and binder are uniformly mixed, obtain mixture, then by the mixture
It is molded, obtains ceramic body；With
(2) ceramic body that step (1) obtains is sintered, high intensity silicon calcium phosphate biological ceramic material is made.
2. preparation method according to claim 1, it is characterised in that：
The mass ratio of the Zinc oxide powder and the silicon calcium phosphate powder is (0.1~5)：(95~99.9), preferably (0.5
~5)：(95~99.5).
3. preparation method according to claim 1, it is characterised in that：
The sintering includes the sintering of the first temperature stage and the sintering of second temperature stage；
The temperature of first temperature stage sintering is 500 DEG C~700 DEG C, time of the first temperature stage sintering is 30~
120min；
The temperature of second temperature stage sintering is 800 DEG C~1400 DEG C, preferably 1100 DEG C~1400 DEG C, more preferably
1250 DEG C~1350 DEG C, the time of the second temperature stage sintering is 30~360min, preferably 60~240min.
4. preparation method according to claim 1, it is characterised in that：
The temperature of sintering is risen to using the heating rate of 1 DEG C/min~10 DEG C/min in step (2).
5. preparation method according to claim 1, it is characterised in that：
The dosage of the binder accounts for 0.1~5wt% of the sum of the Zinc oxide powder and the silicon calcium phosphate powder dosage, excellent
It is selected as 0.1~2wt%.
6. preparation method according to claim 1, it is characterised in that：
The binder is water based adhesive.
7. preparation method according to claim 1, it is characterised in that：
It is uniform by ball milling mixing using water as ball-milling medium in step (1).
8. preparation method according to claim 1, it is characterised in that：
In step (1), the mixture is subjected to dry-pressing formed and cold isostatic compaction successively.
9. preparation method according to claim 8, it is characterised in that：
The dry-pressing formed pressure be 5~100MPa, preferably 10~50MPa, the dry-pressing formed dwell time be 1~
10min, preferably 2~8min；And/or
The pressure of the cold isostatic compaction is 50~400MPa, preferably 100~300MPa, the guarantor of the cold isostatic compaction
The pressure time is 1~10min, preferably 2~8min.
10. according to high intensity silicon calcium phosphate biological ceramic material made from claim 1 to 9 any one of them preparation method；
Preferably, the bending strength of the high intensity silicon calcium phosphate biological ceramic material is not less than 65MPa, and the porosity is less than 5%.
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