CN104147637B - A kind of construction method of composite ceramic porcelain body rack surface micro-nano hole - Google Patents
A kind of construction method of composite ceramic porcelain body rack surface micro-nano hole Download PDFInfo
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- CN104147637B CN104147637B CN201310176609.XA CN201310176609A CN104147637B CN 104147637 B CN104147637 B CN 104147637B CN 201310176609 A CN201310176609 A CN 201310176609A CN 104147637 B CN104147637 B CN 104147637B
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- hap
- tcp
- porcelain body
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- phosphoric acid
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Abstract
For the current HAP/TCP composite ceramic porcelain body support for repairing bone defect, the present invention proposes and a kind ofly utilize hydroxyapatite and the inconsistent feature of calcium phosphate degradation speed, namely β-TCP and the chemical reaction velocity of phosphoric acid are far away faster than HAP, when adopting phosphoric acid solution corrosion, β-TCP the granule of composite ceramic porcelain body rack surface will be dissolved in phosphoric acid solution, leave micro-void; And HAP granule will corrode on a small quantity, form nanoaperture at grain surface.Final formation is applicable to the surface micronano hole of cell adhesion growth, and the micro-nano hole formed has certain regularity.
Description
Art
The present invention relates to a kind of construction method for hydroxyapatite/tricalcium phosphate composite ceramic porcelain body rack surface micro-nano hole, particularly relate to a kind of bone support prepared for selective laser sintering nanometer hydroxyapatite, tricalcium phosphate mixed-powder, utilize hydroxyapatite and the inconsistent feature of tricalcium phosphate degradation speed, adopt phosphoric acid solution selective corrosion bone support to obtain the method for surperficial micro-nano hole.
Background technology
Along with the average life of people improves constantly, population aging, the Cranial defect that orthopaedic disease causes is in rising trend, and the whole world has every year more than 2,200,000 routine Cranial defect patient with operation.In recent years, along with Biotechnology development is ripe gradually, artificial bone scaffold repairing bone defect is adopted to become possibility.But synosteosis to be formed after artificial bone scaffold implant into body and generally need 1-3 month, even the longer time, therefore be difficult at once or early loading.In order to shorten the synosteosis time of bone support and strengthen synosteosis, bone support need do surface treatment.
The bone support of surface micro-nano hole, compared with ganoid bone support, can provide more active target spot, obtain synosteosis faster, form larger synosteosis interface and stronger anti-shear ability.Cell culture verification table mask has the smooth bone support of the bone support specific surface of micro-nano hole more can increase contact rate and the mechanical bonding force of bone support and osseous tissue simultaneously, more can promote the formation of new bone.The bone support of the surperficial micro-nano hole of same proof has higher survival rate clinically.Therefore the preparation method of bone rack surface micro-nano hole is study hotspot always.
Calcium phosphate biological ceramic is hydroxyapatite (Ca mainly
10(PO
4)
6(OH)
2, Hydroxylaptite, is called for short HAP) and tricalcium phosphate (Ca
3(PO
4)
2, TricalciumPhosphate, is called for short TCP) replace in biomaterial in the sclerous tissues of research and use at present and occupy very large proportion.This is because calcium phosphate biological ceramic has good biocompatibility and biological activity, to human non-toxic, without carcinogenesis, and firmly synosteosis can be carried out with natural bone by the biochemical reaction in body.
But it is large to there is fragility in this kind of material, bending strength is not enough, the unmanageable shortcoming of degradation rate, and composite ceramics has than the better mechanical property of homogenous material and adjustable degradation rate, be therefore more utilize composite ceramic porcelain body support (as HAP/TCP) to carry out repairing bone defect at present.
Summary of the invention
For the current HAP/TCP composite ceramic porcelain body support for repairing bone defect, the present invention proposes and a kind ofly utilize hydroxyapatite and the inconsistent feature of calcium phosphate degradation speed, adopt phosphoric acid solution selective corrosion bone support to obtain the method for surperficial micro-nano hole.The present invention mainly comprises the steps:
(1) composite ceramics support preparation: experiment is with HAP powder purchased from Nanjing Ai Purui nano material company limited, and adopt sol-gel process preparation, minute hand shape, wide about 20nm, is about 150nm, mean diameter 40nm.β-TCP powder is provided by Chinese Kunshan Huaqiao Science and Technology New Materials Co., Ltd, adopts sedimentation method preparation, with Ca (NO
3)
2(NH
4)
2hPO
4for raw material, through 700-800 DEG C of calcining, be incubated 3-5 hour and obtain.Powder is white amorphous powder; Particle mean size 200nm, fusing point 1670 DEG C, bulk density 0.75g/cm
3, Ca/P ratio is 1.50.HAP/ β-TCP the composite powder of different ratio utilizes mechanical mixing mix homogeneously.Composite ceramic porcelain body support utilizes selective laser sintering HAP/ β-TCP composite powder to obtain (Fig. 1).
(2) micro--receiving bore gap structure corrosion: the HAP/ β-TCP composite ceramic porcelain body support of preparation is soaked 7 minutes in the phosphoric acid solution of 2% concentration, selective corrosion process is carried out to rack surface.Corrosion temperature is 30 DEG C, without stirring and rocking during corrosion.Take out support after corrosion, utilize deionized water washing by soaking repeatedly, carry out test analysis 120 DEG C of conditions after dry 3 hours thereafter.Because the chemical reaction velocity of β-TCP and phosphoric acid is far away faster than HAP, the β-TCP granule of composite ceramic porcelain body rack surface will be dissolved in phosphoric acid solution, leave micro-void; And HAP granule will corrode on a small quantity, form nanoaperture (Fig. 2) at grain surface.Along with the increase of β-TCP content in composite ceramics, after corrosion, composite ceramic porcelain body rack surface structure will present regular change (Fig. 3).
(3) micro--receiving bore gap performance test: MG-63 osteosarcoma cell has been carried out to the biology performance of obtained micro-nano hole and has adhered to test and cell counting experiment, show that obtained micro-nano pore structure meets osteoblastic growth and migration: the hole provided and channel space are conducive to sticking of osteocyte, and provide advantage (Fig. 4) for the conveying of nutrient substance and metabolite.
Compared with prior art, advantage of the present invention is:
1., after corrosion, find that surperficial β-TCP corrodes completely, leave micro-void; And the corrosion of HAP generating portion, form nanoaperture at grain surface, finally obtain micro-nano hole;
2. according to contained HAP and β-TCP ratio different control micro--receiving bore gap number, and prepared micro--distribution of receiving bore gap structure has certain regularity;
3. after etching, exposed is HAP acicular grains (Fig. 5) at outer surface, and HAP is conducive to interface forms chemical key being combined with being organized in after in stent implant;
4. prepared micro--receiving bore gap shows good cell adhesion performance;
5. relate to a kind of utilize selective corrosion prepare bone rack surface micro--method of receiving bore gap structure, the method has simple, the easy to operate feature of preparation technology.
Accompanying drawing explanation
Composite ceramics support obtained by Fig. 1
Fig. 2 corrodes the surperficial micro-nano hole of rear composite ceramic porcelain body support
The surperficial micro-nano hole of the different HAP/ β of Fig. 3-TCP ratio composite ceramics
(1) 10% β-TCP content compound rest; (2) 20% β-TCP content compound rests; (3) 30% β-TCP
Content compound rest; (4) 40% β-TCP content compound rests; (5) 50% β-TCP content compound rest Fig. 4 surfaces are micro--the cell adhesion quantity of receiving bore gap
(1) 10% β-TCP content compound rest; (2) 20% β-TCP content compound rests; (3) 30% β-TCP
Content compound rest; (4) 40% β-TCP content compound rests; Energy spectrogram (main component is HAP) of (5) 50% β-TCP content compound rest Fig. 5 surface micro-nano holes
Specific embodiment
Below in conjunction with an embodiment, the specific embodiment of the present invention is further described, but the content of the present invention is not limited thereto.
1) adopt nano-HAP powder and β-TCP powder to be raw material, wherein HAP powder is purchased from Nanjing Ai Purui nano material company limited, and adopt sol-gel process preparation, minute hand shape, wide about 20nm, is about 150nm, mean diameter 40nm.β-TCP powder is provided by Chinese Kunshan Huaqiao Science and Technology New Materials Co., Ltd, adopts sedimentation method preparation, with Ca (NO
3)
2(NH
4)
2hPO
4for raw material, through 700-800 DEG C of calcining, be incubated 3-5 hour and obtain.Powder is white amorphous powder; Particle mean size 200nm, fusing point 1670 DEG C, bulk density 0.75g/cm
3, Ca/P ratio is 1.50.HAP/ β-TCP the composite powder of different ratio obtains after utilizing mechanical mixing to grind 60min.β-TCP/HAP composite powder comprises five kinds of proportionings, and β-TCP mass percent is respectively 10%, 20%, 30%, 40%, 50%.
2) selective laser sintering machine is utilized, at laser power 50W, scanning speed 200mm/min, spot diameter
under the condition of sweep span 1mm and paving powder thickness 0.1mm, according to design sintering path, constituency sintering is carried out to obtained composite powder, carry out lower one deck sintering again after completing one deck, finally prepare the composite ceramic porcelain body support (Fig. 1) with interconnected porous.
3) the HAP/ β-TCP composite ceramic porcelain body support of preparation is soaked 7 minutes in the phosphoric acid solution of 2% concentration, selective corrosion process is carried out to rack surface.Take out support after corrosion, utilize deionized water washing by soaking repeatedly, carry out test analysis (Fig. 2,3) 120 DEG C of conditions after dry 3 hours thereafter.
4) effects on surface hole utilizes MG-63 cell to carry out cell adhesion experiments, and MG-63 cell is provided by American Type Culture preservation center, gets its 100 μ L (concentration 1 × 10
6/ ml) be added drop-wise to rack surface.37 ± 1 DEG C, volume fraction 5%CO
2incubator is cultivated.Every 24h changes culture fluid, carries out cell counting test after 7 days.10%, 20%, 30%, 40%, 50% β-TCP content compound rest unit square millimeter area inner cell quantity is respectively 978,2260,2542,2946,2346 (Fig. 4).
5) carry out EDX energy spectrum analysis to selective corrosion after-poppet specimen surface, surface C a/P ratio is 1.67, matches with the Ca/P ratio of HAP.It can thus be appreciated that the exposed elongated piece of support specimen surface is HAP granule (Fig. 5).
Claims (2)
1. utilize hydroxyapatite and the inconsistent feature of calcium phosphate degradation speed, adopt phosphoric acid solution selective corrosion HAP/ β-TCP composite ceramics support to prepare the method for surperficial micro-nano hole, it is characterized in that: said method comprising the steps of:
(1) utilize the HAP/ β-TCP composite powder of mechanical mixing mix homogeneously different ratio, utilize selective laser sintering HAP/ β-TCP composite powder to obtain composite ceramic porcelain body support;
(2) soaked 7 minutes in the phosphoric acid solution of 2% concentration by the HAP/ β-TCP composite ceramic porcelain body support of preparation, carry out selective corrosion process to rack surface, corrosion temperature is 30 DEG C, without stirring and rocking during corrosion.
2. according to the method described in claim 1, it is characterized in that: the proportioning regulating HAP/ β-TCP composite powder according to required hole, wherein, β-TCP mass percent is 10%, 20%, 30%, 40%, 50%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546177A (en) * | 2003-12-03 | 2004-11-17 | 北京市意华健科贸有限责任公司 | Coral hydroxyapatite artificial bone with betatype tricalcium phosphate coating and its preparation |
| CN1704129A (en) * | 2004-05-28 | 2005-12-07 | 张冬海 | Preparation technique of absorbent hydroxyapatite artificial bone |
| CN101773412A (en) * | 2009-01-09 | 2010-07-14 | 沈阳天贺新材料开发有限公司 | Surface activation method of dental implant |
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| US20050123652A1 (en) * | 2003-12-04 | 2005-06-09 | Kuzma William M. | Method for producing tri-calcium phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546177A (en) * | 2003-12-03 | 2004-11-17 | 北京市意华健科贸有限责任公司 | Coral hydroxyapatite artificial bone with betatype tricalcium phosphate coating and its preparation |
| CN1704129A (en) * | 2004-05-28 | 2005-12-07 | 张冬海 | Preparation technique of absorbent hydroxyapatite artificial bone |
| CN101773412A (en) * | 2009-01-09 | 2010-07-14 | 沈阳天贺新材料开发有限公司 | Surface activation method of dental implant |
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