CN103656737A - Preparation method of HAP/TCP/TTCP (hydroxylapatite/tricalcium phosphate/tetracalcium) multiphase porous ceramic artificial bone - Google Patents
Preparation method of HAP/TCP/TTCP (hydroxylapatite/tricalcium phosphate/tetracalcium) multiphase porous ceramic artificial bone Download PDFInfo
- Publication number
- CN103656737A CN103656737A CN201210358254.1A CN201210358254A CN103656737A CN 103656737 A CN103656737 A CN 103656737A CN 201210358254 A CN201210358254 A CN 201210358254A CN 103656737 A CN103656737 A CN 103656737A
- Authority
- CN
- China
- Prior art keywords
- hap
- tcp
- ttcp
- artificial bone
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention belongs to the field of manufacturing and bone tissue engineering, and particularly relates to a preparation method of HAP/TCP/TTCP (hydroxylapatite/tricalcium phosphate/tetracalcium) multiphase porous ceramic artificial bone. According to the method provided by the invention, the nano HAP powder is selectively sintered with laser, and the characteristic of high energy density of the laser beam can be used to quickly heat the powder layer to high temperature to partially decompose HAP into TCP and TTCP to obtain the HAP/TCP/TTCP multiphase porous ceramic artificial bone. The method has the advantages that the inter-phase conversion time can be controlled by adjusting the laser power and scanning speed to realize adjustment of the content of each phase and achieve an aim of biodegradability regulation. The formed multiphase ceramic artificial bone scaffold has controllable biodegradability and good biocompatibility as well as appearance consistent with the implanting position and interconnected and controllable pore distribution.
Description
Technical field
The invention belongs to and manufacture and bone tissue engineer field, the particularly preparation method of the heterogeneous porous ceramics artificial bone of a kind of HAP/TCP/TTCP.Its method is to utilize the sintering nano-HAP powder of laser selective, the high-energy-density characteristic of laser beam can quickly heat up to high temperature by bisque, make part HAP be decomposed into TCP and TTCP, thereby preparation is by the heterogeneous porous ceramics artificial bone forming of HAP/TCP/TTCP.Can, by regulating laser power and scanning speed to control the transformation time that each thing is alternate, realize the adjusting to phase content in artificial bone, and then reach the regulation and control to its degradation speed simultaneously.
Technical background
At present, the new direction that artificial bone has become medical science and the exploration of bone tissue engineer field is prepared in research.The main target of bone tissue engineer is to build complex structure and degradable artificial bone support, then cell and bone support is carried out to bone defect repair after compound.Bone support, not only for cell provides support structure, keeps former organized shape, but also plays template action, for cell provides the place of the boarding of relying, growth, Differentiation and proliferation, guide tissue regeneration.For making human bone cell in the breeding growth of bone rack surface, bone support is degraded gradually until be completely absorbed in human bone growth, needs artificial bone to meet following requirement: the biocompatibility that (1) is good and bone conductibility; (2) good degradability and adjustable degradation rate; (3) there is the three-dimensional porous structure of interconnection.
Calcium phosphate biological ceramic has good biocompatibility, can show good affinity with cell, has been widely used as bone tissue engineering stent material.Calcium phosphate biological ceramic mainly comprises hydroxyapatite (Hydroxylaptite, HAP), tricalcium phosphate (Tricalcium phosphate, TCP), tetracalcium phosphate (Tetracalcium, TTCP) and their mixture, its composition and bone mineral composition are similar, can there is degraded in various degree and be absorbed by tissue in them, be therefore considered to most typical bioceramic under biotic environment.The degraded of bone support has important effect to the growth of tissue, if degradation speed is too fast, freshman bone tissue has little time to grow into; And degradation speed is too slow, will hinder the growth of osseous tissue, therefore need the degradation rate of bone support and the growth rate of freshman bone tissue consistent.Due to patient's personalization and the differentiation of osseous tissue, there is adjustable degradation rate and be also very important simultaneously.
HAP has good biological activity, can form firmly bone bonding with human bone, but it is difficult for degraded in vivo; TCP has good osteoinductive, but its degradation speed is in vivo too fast, does not mate with new bone growth speed, and bone support intensity, along with the carrying out of degraded significantly declines, has limited its application clinically.Therefore, homogenous material can not meet bone reparation requirement well.The artificial bone scaffold that utilizes Material cladding of different nature to form, not only has the character of component material concurrently, and can obtain the new capability that single component material does not possess.Research shows that the multiphase ceramics such as HAP/TCP have the toughness of controlled biological property and Geng Gao.The more important thing is and can, by the ratio of HAP and TCP in adjustment bone support, realize the regulation and control to artificial bone degradation speed.
HAP can lose reversible adsorption water lower than 200 ℃, and temperature can further lose the water of strong bonded and change voelckerite into after 800 ℃: Ca
10(PO
4) (OH)
2→ H
2o+Ca
10(PO
4)
6o, is room, Ca
10(PO
4)
6o is voelckerite.Can further there is decomposition reaction: Ca in the HAP at higher temperature
10(PO
4)
6o → 2Ca
3(PO
4)
2+ Ca
4p
2o
9, Ca wherein
3(PO
4)
2for TCP, Ca
4p
2o
9for TTCP.This provides theoretical foundation for utilizing single HAP material to prepare multiphase ceramic artificial bone.Selective laser sintering (Selective Laser Sintering, SLS) be a kind of employing laser layering sintering solid powder selectively, be layering and generate the rapid shaping technique of required form part, can manufacture complicated profile and interconnected three-dimensional porous structure.The high-energy-density characteristic of laser beam can quickly heat up to high temperature by bisque, makes part HAP be converted into TCP and TTCP.The more important thing is, by controlling laser technical parameters, can realize the control to the thing inversion of phases time, be expected to realize the adjusting to phase content in artificial bone.
Therefore, the present invention proposes to utilize the single HAP powder of sintering of high-energy-density laser selective, and preparation is by the heterogeneous porous ceramics artificial bone forming of HAP/TCP/TTCP.By regulating laser power and scanning speed to control the transformation time that each thing is alternate, realize the adjusting to phase content in artificial bone, this makes it have great importance with new bone growth speed is consistent for regulation and control artificial bone degradation speed simultaneously.
Summary of the invention
The present invention proposes the method that the single HAP material of a kind of SLS of utilization technology sintering is prepared the heterogeneous porous artificial bone scaffold of HAP/TCP/TTCP, mainly comprises the following steps:
(1) HAP powder is placed in the SLS system of development voluntarily, by the profile requirement in defective bone cross section, with necessarily sintering is apart from interval, control laser is sintered powder selectively.After sintering one deck, the workbench layer thickness that declines, then carry out stone and the sintering of lower one deck, and be layering like this, finally realize the sinter molding of ceramic artificial bone.
(2) adjust laser technical parameters (laser power and scanning speed) sintering nano-HAP powder respectively, by controlling sintering time (scanning speed), control the decomposition of HAP, prepare the HAP/TCP/TTCP multiphase ceramic artificial bone that different phase contents form.
(3) workbench certain height that declines, takes off artificial bone utilize from workbench the equipment such as hairbrush and air gun to remove after unsintered powder, obtains having the HAP/TCP/TTCP multiphase ceramic artificial bone of three-dimensional porous structure.
The invention has the advantages that:
1, utilize the sintering nano-HAP powder of laser selective, the high temperature that the high-energy-density characteristic by laser produces makes part HAP be decomposed into TCP and TTCP, thereby prepares the porous ceramics artificial bone that contains HAP/TCP/TTCP three-phase;
2,, according to implant site requirement, by adjusting sintering process parameter, can control the content of each composition of HAP/TCP/TTCP in prepared ceramic artificial bone, thereby realize the regulation and control to biodegradation rate;
3, the preparation method that has proposed the heterogeneous porous ceramics artificial bone of a kind of HAP/TCP/TTCP, has production efficiency high, feature with short production cycle.
Accompanying drawing explanation
Fig. 1 is the heterogeneous porous ceramics artificial bone scaffold utilizing after SLS technology sintering.
Fig. 2 is laser power 20W, the XRD figure spectrum of the prepared support of scanning speed 100mm/min.
Fig. 3 is laser power 20W, the XRD figure spectrum of the prepared support of scanning speed 500mm/min.
Fig. 4 is laser power 20W, the XRD figure spectrum of the prepared support of scanning speed 800mm/min.
The specific embodiment
Below by example, the specific embodiment of the present invention is described further.
Adopt nanometer hydroxyapatite powder stock, wherein HAP is minute hand shape, is about 150nm, wide about 20nm, mean diameter 40nm.Based on independently developed selective laser sintering system (ZL200910043210.8), under the process conditions of laser spot diameter 1mm, paving powder thickness 0.2mm, laser power 20W, scanning speed 100mm/min, HAP powder is carried out to selective sintering, the three-dimensional porous artificial bone scaffold of the sinter molding that is layering.
Utilize XRD to analyze the support of preparation, prepared support composition is:
HAP∶TCP∶TTCP＝65∶24∶11
Adopt nanometer hydroxyapatite powder stock, wherein HAP is minute hand shape, is about 150nm, wide about 20nm, mean diameter 40nm.Based on independently developed selective laser sintering system, under the process conditions of laser spot diameter 1mm, paving powder thickness 0.2mm, laser power 20W, scanning speed 500mm/min, HAP powder is carried out to selective sintering, the three-dimensional porous artificial bone scaffold of the sinter molding that is layering.
Utilize XRD to analyze the support of preparation, prepared support composition is:
HAP∶TCP∶TTCP＝72∶20∶8
Adopt nanometer hydroxyapatite powder stock, wherein HAP is minute hand shape, is about 150nm, wide about 20nm, mean diameter 40nm.Based on independently developed selective laser sintering system, under the process conditions of laser spot diameter 1mm, paving powder thickness 0.2mm, laser power 15W, scanning speed 800mm/min, HAP powder is carried out to selective sintering, the three-dimensional porous artificial bone scaffold of the sinter molding that is layering.
Utilize XRD to analyze the support of preparation, prepared support composition is:
HAP∶TCP∶TTCP＝86∶11∶3。
Claims (4)
1. utilize the single HAP material of SLS technology sintering to prepare a method for the heterogeneous porous artificial bone scaffold of HAP/TCP/TTCP, mainly comprise the following steps:
(1) HAP powder is placed in the SLS system of development voluntarily, by the profile requirement in defective bone cross section and certain sintering apart from interval, control laser sintered powder selectively, after sintering one deck, a layer thickness of workbench decline, the stone and the sintering that carry out lower one deck, be layering so again, finally realizes the sinter molding of ceramic artificial bone;
(2) adjust laser technical parameters (laser power and scanning speed) sintering nano-HAP powder respectively, by controlling sintering time (scanning speed), control the decomposition of HAP, prepare the HAP/TCP/TTCP multiphase ceramic artificial bone that different phase contents form;
(3) workbench certain height that declines, takes off artificial bone utilize from workbench the equipment such as hairbrush and air gun to remove after unsintered powder, obtains having the HAP/TCP/TTCP multiphase ceramic artificial bone of three-dimensional porous structure.
2. preparation method according to claim 1, it is characterized in that: the sintering nano-HAP powder that utilizes laser selective, the high temperature that high-energy-density characteristic by laser produces makes part HAP be decomposed into TCP and TTCP, thereby prepares the porous ceramics artificial bone that contains HAP/TCP/TTCP three-phase.
3. preparation method according to claim 1, it is characterized in that: according to implant site requirement, by adjusting sintering process parameter, can control the content of each composition of HAP/TCP/TTCP in prepared ceramic artificial bone, thereby realize the regulation and control to biodegradation rate.
4. preparation method according to claim 1, is characterized in that: proposed the preparation method of the heterogeneous porous ceramics artificial bone of a kind of HAP/TCP/TTCP, had production efficiency high, feature with short production cycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210358254.1A CN103656737A (en) | 2012-09-25 | 2012-09-25 | Preparation method of HAP/TCP/TTCP (hydroxylapatite/tricalcium phosphate/tetracalcium) multiphase porous ceramic artificial bone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210358254.1A CN103656737A (en) | 2012-09-25 | 2012-09-25 | Preparation method of HAP/TCP/TTCP (hydroxylapatite/tricalcium phosphate/tetracalcium) multiphase porous ceramic artificial bone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103656737A true CN103656737A (en) | 2014-03-26 |
Family
ID=50296290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210358254.1A Pending CN103656737A (en) | 2012-09-25 | 2012-09-25 | Preparation method of HAP/TCP/TTCP (hydroxylapatite/tricalcium phosphate/tetracalcium) multiphase porous ceramic artificial bone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103656737A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106344966A (en) * | 2015-07-13 | 2017-01-25 | 中南大学 | Method for improving cell adhesion of polyglycolic acid stent by using mesoporous silica |
| WO2017092713A1 (en) * | 2015-12-04 | 2017-06-08 | 高雄医学大学 | Method for additive manufacturing of 3d-printed articles |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507839A (en) * | 2009-03-27 | 2009-08-19 | 陕西科技大学 | Preparation method of bionic human bone biologic material |
| CN101530950A (en) * | 2009-04-24 | 2009-09-16 | 中南大学 | Laser sintering machine based on nano hydroxyapatite and used for manufacturing absorptive artificial bone |
| CN101880033A (en) * | 2010-03-04 | 2010-11-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing calcium phosphate for biological ceramics |
| CN101991876A (en) * | 2009-08-14 | 2011-03-30 | 机械科学研究总院先进制造技术研究中心 | Manufacture method of prosthesis with self-antibacterial action |
-
2012
- 2012-09-25 CN CN201210358254.1A patent/CN103656737A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507839A (en) * | 2009-03-27 | 2009-08-19 | 陕西科技大学 | Preparation method of bionic human bone biologic material |
| CN101530950A (en) * | 2009-04-24 | 2009-09-16 | 中南大学 | Laser sintering machine based on nano hydroxyapatite and used for manufacturing absorptive artificial bone |
| CN101991876A (en) * | 2009-08-14 | 2011-03-30 | 机械科学研究总院先进制造技术研究中心 | Manufacture method of prosthesis with self-antibacterial action |
| CN101880033A (en) * | 2010-03-04 | 2010-11-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing calcium phosphate for biological ceramics |
Non-Patent Citations (2)
| Title |
|---|
| CIJUN SHUAI ET AL.: ""Structure and properties of nano-hydroxypatite scaffolds for bone tissue engineering with a selective laser sintering system", 《NANOTECHNOLOGY》, vol. 22, no. 28, 6 June 2011 (2011-06-06), XP020206971, DOI: doi:10.1088/0957-4484/22/28/285703 * |
| CIJUN SHUAI ET AL.: "Simulation of dynamic temperature field during selective laser sintering of ceramic powder", 《MATHEMATICAL AND COMPUTER MODELLING OF DYNAMICAL SYSTEMS: METHODS, TOOLS AND APPLICATIONS IN ENGINEERING AND RELATED SCIENCES》, vol. 19, no. 1, 25 May 2012 (2012-05-25), pages 1 - 11 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106344966A (en) * | 2015-07-13 | 2017-01-25 | 中南大学 | Method for improving cell adhesion of polyglycolic acid stent by using mesoporous silica |
| WO2017092713A1 (en) * | 2015-12-04 | 2017-06-08 | 高雄医学大学 | Method for additive manufacturing of 3d-printed articles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Biomedical applications of the powder‐based 3D printed titanium alloys: a review | |
| Brunello et al. | Powder-based 3D printing for bone tissue engineering | |
| Shuai et al. | Structure and properties of nano-hydroxypatite scaffolds for bone tissue engineering with a selective laser sintering system | |
| CN105196398B (en) | For the ceramic slurry of air pressure extruded type 3 D-printing and the preparation method of bioceramic scaffold | |
| Gross et al. | Biodegradable composite scaffolds with an interconnected spherical network for bone tissue engineering | |
| Sánchez-Salcedo et al. | Upgrading calcium phosphate scaffolds for tissue engineering applications | |
| Karamian et al. | Fabrication of hydroxyapatite-baghdadite nanocomposite scaffolds coated by PCL/Bioglass with polyurethane polymeric sponge technique | |
| JP2003507132A (en) | Resorbable bone substitutes and bone constituents | |
| CN105582571A (en) | Manufacturing method of high-strength bioactive porous scaffold | |
| CN102796910B (en) | Method for preparing porous tantalum medical implant material through selective laser sintering forming | |
| Shuai et al. | Structural design and experimental analysis of a selective laser sintering system with nano-hydroxyapatite powder | |
| CN103585677B (en) | A kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application | |
| CN103638556B (en) | A kind of making Nano surface modified phosphate calcium bioactive ceramics and Synthesis and applications thereof | |
| CN103467104B (en) | Method for improving ceramic sintering performance by adding a small amount of polylactic acid in artificial bone prepared by laser | |
| KR20180003110A (en) | Porous bone substitutes and method for producing thereof | |
| CN101766843A (en) | Artificial bone with porous laminated structure and passages and preparation method thereof | |
| CN108348637B (en) | Large 3D porous scaffold made from active hydroxyapatite obtained by biomorphic transformation of natural structure and process for obtaining same | |
| Salimi | Functionally graded calcium phosphate bioceramics: An overview of preparation and properties | |
| CN102851664B (en) | Method for preparing hydroxy apatite biological ceramic coating containing fluorine | |
| CN103656737A (en) | Preparation method of HAP/TCP/TTCP (hydroxylapatite/tricalcium phosphate/tetracalcium) multiphase porous ceramic artificial bone | |
| CN105477687B (en) | A kind of porous artificial bone and preparation method thereof | |
| Havlik et al. | Hydroxyapatite | |
| Miri et al. | Review on the strategies to improve the mechanical strength of highly porous bone bioceramic scaffolds | |
| CN1613435A (en) | Photocureable rapid shaping indirect manufacturing method for controllable microtube structure stand | |
| Umemoto et al. | In vivo bioresorbability and bone formation ability of sintered highly pure calcium carbonate granules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140326 |
|
| RJ01 | Rejection of invention patent application after publication |