CN104147637A - Construction method for composite ceramic bone scaffold surface micro-nano pores - Google Patents
Construction method for composite ceramic bone scaffold surface micro-nano pores Download PDFInfo
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- CN104147637A CN104147637A CN201310176609.XA CN201310176609A CN104147637A CN 104147637 A CN104147637 A CN 104147637A CN 201310176609 A CN201310176609 A CN 201310176609A CN 104147637 A CN104147637 A CN 104147637A
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Abstract
The invention provides a construction method aimed at an HAP/TCP composite ceramic bone scaffold used for repairing bone defect at present. The characteristic is utilized that the degradation velocities of hydroxylapatite and calcium phosphate are different, namely the chemical reaction velocity of beta-TCP and phosphoric acid is far faster than the chemical reaction velocity of HAP and phosphoric acid. When corrosion is carried out by utilization of a phosphoric acid, the beta-TCP particles on the composite ceramic bone scaffold surface are dissolved in the phosphoric acid, and micro-pores are formed; HAP particles are corroded slightly and nano pores are formed on the crystal grain surface. The surface micro-nano pores which are suitable for cell adhesion growth are formed finally, and the formed micro-nano pores have a certain regularity.
Description
Affiliated technical field
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 of preparing 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 people's average life improves constantly, population aging, the bone that orthopaedic disease causes is damaged in rising trend, and the whole world has the damaged patient with operation of 2,200,000 routine bone of surpassing every year.In recent years, along with Biotechnology development is ripe gradually, adopt artificial bone scaffold repairing bone defect to become possibility.But will form synosteosis after artificial bone scaffold implant into body, generally need 1-3 month, even the longer time, be therefore difficult at once or early loading.In order to shorten the synosteosis time of bone support and to strengthen synosteosis, bone support need be done surface treatment.
The bone support of surface micro-nano hole is compared with ganoid bone support, and more active target spot can be provided, and obtains synosteosis faster, forms larger synosteosis interface and stronger anti-shear ability.Cell culture verification table mask has the smooth bone support of bone support specific surface of micro-nano hole more can increase contact rate and the mechanical bond power 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 mainly hydroxyapatite (Ca
10(PO
4)
6(OH)
2, Hydroxylaptite, is called for short HAP) and tricalcium phosphate (Ca
3(PO
4)
2, Tricalcium Phosphate, is called for short TCP) and in replacing biomaterial, the sclerous tissues of research at present and use occupies very large proportion.This is because calcium phosphate biological ceramic has good biocompatibility and biological activity, nontoxic to human body, without carcinogenesis, and can by the biochemical reaction in body, carry out firmly synosteosis with natural bone.
But this class material exists fragility large, 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, is therefore more to 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 a kind of hydroxyapatite and inconsistent feature of calcium phosphate degradation speed utilized, 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 purchased from Nanjing Ai Purui nano material company limited, adopts sol-gel process preparation with HAP powder, 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 ℃ of calcining, be incubated and make for 3-5 hour.Powder is white amorphous powder; Particle mean size 200nm, 1670 ℃ of fusing points, bulk density 0.75g/cm
3, Ca/P ratio is 1.50.HAP/ β-TCP composite powder of different proportionings is to utilize mechanical mixing mix homogeneously.Composite ceramic porcelain body support is to utilize selective laser sintering HAP/ β-TCP composite powder to make (Fig. 1).
(2) micro--Na pore structure corrosion: HAP/ β-TCP composite ceramic porcelain body support of preparation is soaked 7 minutes in the phosphoric acid solution of 2% concentration, rack surface is carried out to selective corrosion processing.Corrosion temperature is 30 ℃, during corrosion without stirring and rocking.After corrosion, take out support, utilize deionized water washing by soaking repeatedly, 120 ℃ of conditions, after dry 3 hours, carry out test analysis thereafter.Because the chemical reaction velocity of β-TCP and phosphoric acid is far away faster than HAP, β-TCP granule of composite ceramic porcelain body rack surface will be dissolved in phosphoric acid solution, leave a micron hole; And HAP granule will corrode on a small quantity, at grain surface, form nanoaperture (Fig. 2).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--Na pore property test: the biology performance of prepared micro-nano hole has been carried out to MG-63 osteosarcoma cell and adhered to test and cell counting experiment, show that prepared micro-nano pore structure meets osteoblastic growth and migration: the hole providing 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, leaves a micron hole; And there is partial corrosion in HAP, at grain surface, form nanoaperture, finally obtain micro-nano hole;
2. according to contained HAP and β-TCP ratio different control micro--Na hole number, and prepared micro--Na pore structure distributes and has certain regularity;
3. after etching, exposed outer surface be HAP acicular grains (Fig. 5), and HAP is conducive to support, forms chemical key after implanting on being organized in interface and be combined;
4. prepared micro--Na hole shown good cell adhesion performance;
5. relate to a kind of utilize selective corrosion prepare bone rack surface micro--method of Na pore structure, the method has simple, the easy to operate feature of preparation technology.
Accompanying drawing explanation
The prepared composite ceramics support of 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-TCP of Fig. 3 ratio composite ceramics
(1) 10% β-TCP content compound rest; (2) 20% β-TCP content compound rest; (3) 30% β-TCP
Content compound rest; (4) 40% β-TCP content compound rest; (5) 50% β-TCP content compound rest Fig. 4 surface is micro--the cell adhesion quantity of Na hole
(1) 10% β-TCP content compound rest; (2) 20% β-TCP content compound rest; (3) 30% β-TCP
Content compound rest; (4) 40% β-TCP content compound rest; The energy spectrogram (main component is HAP) of (5) 50% β-TCP content compound rest Fig. 5 surface micro-nano hole
Specific embodiment
Below in conjunction with an embodiment, the specific embodiment of the present invention is further described, but holds and be not limited to this within the present invention.
1) adopting nano-HAP powder and β-TCP powder is raw material, and wherein HAP powder, purchased from Nanjing Ai Purui nano material company limited, adopts sol-gel process preparation, minute hand shape, and 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 ℃ of calcining, be incubated and make for 3-5 hour.Powder is white amorphous powder; Particle mean size 200nm, 1670 ℃ of fusing points, bulk density 0.75g/cm
3, Ca/P ratio is 1.50.HAP/ β-TCP composite powder of different proportionings 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) utilize selective laser sintering machine, 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, prepared composite powder is carried out to constituency sintering, carry out again lower one deck sintering after completing one deck, finally prepare the composite ceramic porcelain body support (Fig. 1) with interconnection porous.
3) HAP/ β-TCP composite ceramic porcelain body support of preparation is soaked 7 minutes in the phosphoric acid solution of 2% concentration, rack surface is carried out to selective corrosion processing.After corrosion, take out support, utilize deionized water washing by soaking repeatedly, 120 ℃ of conditions, after dry 3 hours, carry out test analysis (Fig. 2,3) thereafter.
4) effects on surface hole utilizes MG-63 cell to carry out cell adhesion experiment, and MG-63 cell is provided by U.S. representative microbial DSMZ, gets its 100 μ L (concentration 1 * 10
6/ ml) be added drop-wise to rack surface.37 ± 1 ℃, 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) selective corrosion after-poppet specimen surface is carried out to EDX energy spectrum analysis, surface C a/P ratio is 1.67, matches with the Ca/P ratio of HAP.Hence one can see that, and the exposed elongated piece of support specimen surface is HAP granule (Fig. 5).
Claims (6)
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 surperficial micro-nano hole, reach the object that promotes cell adhesion and growth.
(1) utilize HAP/ β-TCP composite powder of the different proportionings of mechanical mixing mix homogeneously.Utilize selective laser sintering HAP/ β-TCP composite powder to make composite ceramic porcelain body support.
(2) HAP/ β-TCP composite ceramic porcelain body support of preparation is soaked 7 minutes in the phosphoric acid solution of 2% concentration, rack surface is carried out to selective corrosion processing.Corrosion temperature is 30 ℃, during corrosion without stirring and rocking.
2. according to the method described in claim 1, it is characterized in that: phosphoric acid solution concentration is 2%, soak time is 7 minutes, and corrosion temperature is 30 ℃, during corrosion without stirring and rocking.
3. according to the method described in claim 1, it is characterized in that: can how much regulate according to the hole of required preparation the proportioning of HAP/ β-TCP composite powder, as β-TCP mass percent is respectively 10%, 20%, 30%, 40%, 50%.
4. according to the method described in claim 1, it is characterized in that: support specimen surface β-TCP is corroded, and exposed is HAP granule, after being conducive to support and implanting, form chemical key on being organized in interface and be combined.
5. according to the method described in claim 1, it is characterized in that: prepared surperficial micro-nano hole, be conducive to adhesion and the growth of cell, during by MG-63 cell adhesion experiment table, cell adhesion quantity has increased more than one times.
6. according to the method described in claim 1, it is characterized in that: utilize phosphoric acid solution selective corrosion HAP/ β-TCP composite ceramics support to prepare surperficial micro-nano hole, prepared micro--Na pore structure distributes and has certain regularity.
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| CN201310176609.XA CN104147637B (en) | 2013-05-14 | 2013-05-14 | A kind of construction method of composite ceramic porcelain body rack surface micro-nano hole |
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Citations (4)
| 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 |
| US20050123652A1 (en) * | 2003-12-04 | 2005-06-09 | Kuzma William M. | Method for producing tri-calcium phosphate |
| 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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2013
- 2013-05-14 CN CN201310176609.XA patent/CN104147637B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| US20050123652A1 (en) * | 2003-12-04 | 2005-06-09 | Kuzma William M. | Method for producing tri-calcium phosphate |
| 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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