CN105617456A - Method for preparing lower jawbone repairing material by virtue of 3D (Three-Dimensional) printing - Google Patents

Method for preparing lower jawbone repairing material by virtue of 3D (Three-Dimensional) printing Download PDF

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Publication number
CN105617456A
CN105617456A CN201511034040.9A CN201511034040A CN105617456A CN 105617456 A CN105617456 A CN 105617456A CN 201511034040 A CN201511034040 A CN 201511034040A CN 105617456 A CN105617456 A CN 105617456A
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printing
support
nitrate solution
tcp
prepared
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魏坤
梁猛
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/12Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/045Cobalt or cobalt alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00Processes of additive manufacturing
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/18Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Transplantation (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a method for preparing a lower jawbone repairing material by virtue of 3D (Three-Dimensional) printing. According to the method, beta-tricalcium phosphate (beta-TCP) containing cobalt is prepared by virtue of a liquid phase precipitation method, and a corresponding bone scaffold is prepared according to a printing model by virtue of a 3D printing technology and used for damaged parts of a lower jawbone. Cobalt is adopted to enhance the biocompatibility of the repairing scaffold, and calcium and phosphonium ions in beta-TCP can also be directly used for repairing lower jawbone.

Description

A kind of method that mandible growth material is prepared in 3D printing
Technical field
The present invention relates to the preparation field of mandible growth material, be specifically related to a kind of method that mandible growth material is prepared in 3D printing.
Background technology
Mandibular bone is not only maintenance face contour and form, also chew with patient, pronounce, speech etc. closely related. Because of tumor, injure mandibular defect caused by the factors such as infection outward, affect the facial appearance of patient all to some extent, and affect corresponding oral cavity function.
In bone renovating material, ceramic-like materials has good medical physics and chemistry and biocompatibility, is a kind of bone substitute preferably. Representative is hydroxyapatite and tricalcium phosphate. Wherein tricalcium phosphate has the characteristic of bone conduction to contribute to new bone formation, and has potentially served as calcium deposit effect in new bone formation. Metallic cobalt, as traditional bone renovating material, has good corrosion resistance and cell compatibility.
The present invention, for be combined by two kinds of bone renovating materials, by the preparation of 3d printing technique for the recovery support of mandibular bone, overcomes the shortcoming that the monoblock shape support specific surface area in clinical practice is little, promotes the using value of bone repairing support.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method that mandible growth material is prepared in 3D printing, the method is by first preparing ��-TCP/Co powder body material, according to 3d printer model, prepares ��-TCP/Co support for mandible growth.
The present invention is achieved through the following technical solutions.
A kind of method that mandible growth material is prepared in 3D printing, comprises the following steps:
1) configuration calcium nitrate solution;
2) configuration ammonium dihydrogen phosphate;
3) weigh cobalt nitrate and join in deionized water, obtain cobalt nitrate solution;
4) ammonium dihydrogen phosphate and calcium nitrate solution are measured, the ratio mixing being 1.65 ~ 1.69 with Ca/P mol ratio, control pH between 7 ~ 8, obtain mixed liquor;
5) taking cobalt nitrate solution and be added dropwise in the middle of the mixed liquor of step 4), pH controls between 7 ~ 8;
6) step 5) gained mixed liquor is stirred and stands 22 ~ 26h after 20 ~ 40min, centrifugal within 15 ~ 20 minutes, be precipitated thing, by precipitate washes of absolute alcohol 1 ~ 3 time;
7) by washed precipitate in an oven 95 ~ 105 DEG C dry 5 ~ 6 hours;
8) dried precipitate is ground, then calcines 2 ~ 3 hours at 850 ~ 950 DEG C;
9) use ethanol wet ball-milling 6 ~ 7 hours after calcining, obtain ��-TCP/Co composite granule;
10) taking in 0.4 ~ 0.6gPVA to 45 ~ 55ml deionized water, heated and stirred is all dissolved to PVA, is cooled to room temperature, obtains PVA solution;
11) 0.4 ~ 0.6g ��-TCP/Co composite granule is added in the PVA solution of 0.8 ~ 1.2ml, and is stirred continuously to thick;
12) designing stent model with 3dsmax, the base diameter of support is 8 ~ 12mm, height is 2.5 ~ 3.5mm, and lines broadband and line pitch are 240 ~ 260 ��m;
13) thick for step 11) gained product is carried out support printing as printed material;
14) support of printing is positioned in high temperature furnace at 580 ~ 620 DEG C and calcines 1.5 ~ 2.5h, remove PVA, obtain ��-TCP/Co support.
Further, in step 1), calcium nitrate 9.450g ~ 10.000g, deionized water 180 ~ 220ml in described calcium nitrate solution.
Further, step 2) ammonium dihydrogen phosphate 4.600g ~ 5.000g, deionized water 180 ~ 220ml in described ammonium dihydrogen phosphate.
Further, cobalt nitrate described in step 3) is 1.81 ~ 1.85g, and deionized water is 95 ~ 105ml.
Further, ammonium dihydrogen phosphate described in step 4) is 28 ~ 32ml, and calcium nitrate solution is 48 ~ 52ml.
Further, cobalt nitrate solution described in step 5) is 6.4 ~ 6.6ml.
Further, a kind of method that mandible growth material is prepared in 3D printing, comprise the following steps:
1. configure the calcium nitrate solution of the 0.2mol/l of 200ml;
2. configure the ammonium dihydrogen phosphate of the 0.2mol/l of 200ml;
3. weigh 1.83g cobalt nitrate to join in 100ml deionized water, obtain 0.1mol/l cobalt nitrate solution;
4. measure 30ml0.2mol/l ammonium dihydrogen phosphate and 50ml0.2mol/l calcium nitrate solution, the ratio mixing being 1.67 with Ca/P mol ratio, control pH 7.5;
5. taking 6.5ml cobalt nitrate solution and be added dropwise in the middle of the mixed liquor of step 4, pH controls 7.5;
6. stirring stood 24 hours after half an hour, centrifugal within 20 minutes, was precipitated thing, by precipitate washes of absolute alcohol 2 times;
7. washed precipitate at 100 DEG C dry 6 hours in an oven;
8. dried precipitate is ground, and then calcines 2 hours at 900 DEG C;
9. use ethanol wet ball-milling 6 hours after calcining, obtain ��-TCP/Co composite granule.
10. take 0.5gPVA(polyvinyl alcohol) to 50ml deionized water, heated and stirred is all dissolved to PVA, is cooled to room temperature.
11.0.5g ��-TCP/Co composite granule is added in the PVA solution of 1.0ml, and is stirred continuously to thick.
12. design stent model with 3dsmax, the base diameter of support is 10mm, high for 3mm, and lines broadband and line pitch are 250 ��m.
13. thick for step 11 gained product is carried out support printing as printed material.
Calcine 2 hours 14. the support of printing is positioned in high temperature furnace at 600 DEG C, remove PVA, obtain ��-TCP/Co support.
The present invention contains the �� type tricalcium phosphate (��-TCP) of cobalt by liquid-phase precipitation method preparation, prepares corresponding bone support by 3D printing technique according to printer model, for the defect of mandibular bone. Strengthen the biocompatibility of recovery support by introducing cobalt, and in ��-TCP rich in calcium and phosphonium ion can also be directly used in the reparation of mandibular bone.
Compared with prior art, the present invention has the following advantages that and technique effect:
1) Co is successfully added in the middle of ��-TCP by the present invention, improves the cell compatibility of ��-TCP.
2) present invention use 3d printing technique can the porosity of lifting bracket, relatively conventional bulk shape support is compared, and specific surface area increases, and is conducive to cell to grow to internal stent.
Accompanying drawing explanation
Fig. 1 is the comparison diagram of the cell compatibility of the support that embodiment 1 prepares with embodiment 2;
Fig. 2 is the comparison diagram of the space connected ratio of the ��-TCP support in different lines gap.
Detailed description of the invention
Below in conjunction with embodiment, embodiments of the present invention are further explained explanation, but the present invention is not done any restriction by specific embodiment.
Embodiment 1
1. configure the calcium nitrate solution of 200ml0.2mol/l;
2. configure the ammonium dihydrogen phosphate of 200ml0.2mol/l;
3. weigh 1.83g cobalt nitrate to join in 100ml deionized water, obtain 0.1mol/l cobalt nitrate solution;
4. measuring 30ml0.2mol/l ammonium dihydrogen phosphate and 50ml0.2mol/l calcium nitrate solution, with the Ca/P mixed in molar ratio being 1.67, controlling pH is 7.5, obtains mixed liquor;
5. taking 6.5ml0.1mol/l cobalt nitrate solution and be added dropwise in the middle of the mixed liquor of step 4, pH is 7.5;
6. stirring stood 24 hours after half an hour, centrifugal within 20 minutes, was precipitated thing, by precipitate washes of absolute alcohol 2 times;
7. by washed precipitate in an oven 100 DEG C dry 6 hours;
8. dried precipitate is ground, and then calcines 2 hours at 900 DEG C;
9. use ethanol wet ball-milling 6 hours after calcining, obtain ��-TCP/Co composite granule.
10. take 0.5gPVA(polyvinyl alcohol) add in 50ml deionized water, heat and all dissolve to PVA to 100 DEG C and stirring, be cooled to room temperature.
11. 0.5g ��-TCP/Co composite granule is added in the PVA solution of 1.0ml, and it is stirred continuously to thick.
12. design stent model with 3dsmax, the base diameter of support is 10mm, high for 3mm, and lines broadband and line pitch are 250 ��m.
13. thick for step 11 gained product is carried out support printing as printed material.
Calcine 2 hours 14. the support of printing is positioned in high temperature furnace at 600 DEG C, remove PVA, obtain ��-TCP/Co support.
Embodiment 2
1. configure the calcium nitrate solution of 200ml0.2mol/l;
2. configure the ammonium dihydrogen phosphate of 200ml0.2mol/l;
3. measuring 30ml0.2mol/l ammonium dihydrogen phosphate and 50ml0.2mol/l calcium nitrate solution, with the Ca/P mixed in molar ratio being 1.67, controlling pH is 7.5;
4. stirring stood 24 hours after half an hour, centrifugal within 20 minutes, was precipitated thing, by precipitate washes of absolute alcohol 2 times;
5. by washed precipitate in an oven 100 DEG C dry 6 hours;
6. dried precipitate is ground, then calcines 2 hours at 900 DEG C;
7. use ethanol wet ball-milling 6 hours after calcining, obtain ��-TCP composite granule.
8. take 0.5gPVA(polyvinyl alcohol) add in 50ml deionized water, heat and all dissolve to PVA to 100 DEG C and stirring, be cooled to room temperature.
9. 0.5g ��-TCP composite granule is added in the PVA solution of 1.0ml, and is stirred continuously to thick.
10. designing stent model with 3dsmax, the base diameter of support is 10mm, high for 3mm, and lines broadband and line pitch are 250 ��m.
11. thick for step 9 gained product is carried out support printing as printed material.
Calcine 2 hours 12. the support of printing is positioned in high temperature furnace at 600 DEG C, remove PVA, obtain ��-TCP support.
Embodiment 3
1. configure the calcium nitrate solution of 200ml0.2mol/l;
2. configure the ammonium dihydrogen phosphate of 200ml0.2mol/l;
3. measuring 30ml0.2mol/l ammonium dihydrogen phosphate and 50ml0.2mol/l calcium nitrate solution, with the Ca/P mixed in molar ratio being 1.67, controlling pH is 7.5;
4. stirring stood 24 hours after half an hour, centrifugal within 20 minutes, was precipitated thing, by precipitate washes of absolute alcohol 2 times;
5. by washed precipitate in an oven 100 DEG C dry 6 hours;
6. dried precipitate is ground, then calcines 2 hours at 900 DEG C;
7. use ethanol wet ball-milling 6 hours after calcining, obtain ��-TCP composite granule.
8. take 0.5gPVA(polyvinyl alcohol) add in 50ml deionized water, heat and all dissolve to PVA to 100 DEG C and stirring, be cooled to room temperature.
9. 0.5g ��-TCP composite granule is added in the PVA solution of 1.0ml, and is stirred continuously to thick.
10. designing stent model with 3dsmax, the base diameter of support is 10mm, high for 3mm, and lines broadband and line pitch are 240 ��m.
11. thick for step 9 gained product is carried out support printing as printed material.
Calcine 2 hours 12. the support of printing is positioned in high temperature furnace at 600 DEG C, remove PVA, obtain ��-TCP support.
Embodiment 4
1. configure the calcium nitrate solution of 200ml0.2mol/l;
2. configure the ammonium dihydrogen phosphate of 200ml0.2mol/l;
3. measuring 30ml0.2mol/l ammonium dihydrogen phosphate and 50ml0.2mol/l calcium nitrate solution, with the Ca/P mixed in molar ratio being 1.67, controlling pH is 7.5;
4. stirring stood 24 hours after half an hour, centrifugal within 20 minutes, was precipitated thing, by precipitate washes of absolute alcohol 2 times;
5. by washed precipitate in an oven 100 DEG C dry 6 hours;
6. dried precipitate is ground, then calcines 2 hours at 900 DEG C;
7. use ethanol wet ball-milling 6 hours after calcining, obtain ��-TCP composite granule.
8. take 0.5gPVA(polyvinyl alcohol) add in 50ml deionized water, heat and all dissolve to PVA to 100 DEG C and stirring, be cooled to room temperature.
9. 0.5g ��-TCP composite granule is added in the PVA solution of 1.0ml, and is stirred continuously to thick.
10. designing stent model with 3dsmax, the base diameter of support is 10mm, high for 3mm, and lines broadband and line pitch are 260 ��m.
11. thick for step 9 gained product is carried out support printing as printed material.
Calcine 2 hours 12. the support of printing is positioned in high temperature furnace at 600 DEG C, remove PVA, obtain ��-TCP support.
Embodiment 5
Embodiment 1 and embodiment 2 gained two pack support are carried out mBMSC cultivation. After cultivating 1,4 and 7 days, when lucifuge, CCK-8(2-(2-methoxyl group-4-nitrobenzophenone)-3-(4-nitrobenzophenone)-5-(2,4-disulfonic acid benzene)-2H-tetrazolium monosodium salt) it is made into working solution with culture medium according to 10:1 volume ratio. After respectively the cytoskeleton cultivated 1,4 and 7 days being sucked culture medium, it is directly added in 500mlCCK-8 working solution, puts into incubator and cultivate 30 minutes. Piping and druming mixing processed the CCK-8 working solution of cell, drew 100ml to 96 orifice plate, and every hole takes 3 Duplicate Samples, and does not have bubble. Orifice plate is placed on enzyme connection detector and carries out reading, result. As seen from Figure 1, after adding Co, cell number substantially rises, and illustrates that ��-TCP/Co support has good biocompatibility compared with pure ��-TCP support.
Embodiment 6
��-TCP support prepared by embodiment 2, embodiment 3 and embodiment 4 is carried out the analysis of porosity communication rate by the MicrofocusX-RayHARRIER type Micro-CT instrument adopting MetrisUKSystemLTD. Running voltage is 60KV, and electric current is 78 �� A. Being the short transverse scanning bracket from level to level along support in test, every layer thickness is 8.4 ��m. From Fig. 2, show that the porosity communication rate of the support in different lines gap does not have larger difference, porosity communication rate will not be impacted.

Claims (6)

1. the method that mandible growth material is prepared in a 3D printing, it is characterised in that comprise the following steps:
1) configuration calcium nitrate solution;
2) configuration ammonium dihydrogen phosphate;
3) weigh cobalt nitrate and join in deionized water, obtain cobalt nitrate solution;
4) ammonium dihydrogen phosphate and calcium nitrate solution are measured, the ratio mixing being 1.65 ~ 1.69 with Ca/P mol ratio, control pH between 7 ~ 8, obtain mixed liquor;
5) taking cobalt nitrate solution and be added dropwise in the middle of the mixed liquor of step 4), pH controls between 7 ~ 8;
6) step 5) gained mixed liquor is stirred and stands 22 ~ 26h after 20 ~ 40min, centrifugal within 15 ~ 20 minutes, be precipitated thing, by precipitate washes of absolute alcohol 1 ~ 3 time;
7) by washed precipitate in an oven 95 ~ 105 DEG C dry 5 ~ 6 hours;
8) dried precipitate is ground, then calcines 2 ~ 3 hours at 850 ~ 950 DEG C;
9) use ethanol wet ball-milling 6 ~ 7 hours after calcining, obtain ��-TCP/Co composite granule;
10) taking 0.4 ~ 0.6gPVA to add in 45 ~ 55ml deionized water, heated and stirred is all dissolved to PVA, is cooled to room temperature, obtains PVA solution;
11) 0.4 ~ 0.6g ��-TCP/Co composite granule is added in the PVA solution of 0.8 ~ 1.2ml, and is stirred continuously to thick;
12) designing stent model with 3dsmax, the base diameter of support is 8 ~ 12mm, height is 2.5 ~ 3.5mm, and lines broadband and line pitch are 240 ~ 260 ��m;
13) thick for step 11) gained product is carried out support printing as printed material;
14) support of printing is positioned in high temperature furnace at 580 ~ 620 DEG C and calcines 1.5 ~ 2.5h, remove PVA, obtain ��-TCP/Co support.
2. the method that mandible growth material is prepared in a kind of 3D printing according to claim 1, it is characterised in that in step 1), calcium nitrate 9.450g ~ 10.000g, deionized water 180 ~ 220ml in described calcium nitrate solution.
3. the method that mandible growth material is prepared in a kind of 3D printing according to claim 1, it is characterised in that step 2) in, ammonium dihydrogen phosphate 4.600g ~ 5.000g, deionized water 180 ~ 220ml in described ammonium dihydrogen phosphate.
4. the method that mandible growth material is prepared in a kind of 3D printing according to claim 1, it is characterised in that in step 3), described cobalt nitrate is 1.81 ~ 1.85g, and deionized water is 95 ~ 105ml.
5. the method that mandible growth material is prepared in a kind of 3D printing according to claim 1, it is characterised in that in step 4), described ammonium dihydrogen phosphate is 28 ~ 32ml, and calcium nitrate solution is 48 ~ 52ml.
6. the method that mandible growth material is prepared in a kind of 3D printing according to claim 1, it is characterised in that in step 5), described cobalt nitrate solution is 6.4 ~ 6.6ml.
CN201511034040.9A 2015-12-30 2015-12-30 Method for preparing lower jawbone repairing material by virtue of 3D (Three-Dimensional) printing Pending CN105617456A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1686576A (en) * 2005-05-08 2005-10-26 天津大学 Preparation method of beta-TCP/11A composite biological material
CN101157045A (en) * 2007-10-26 2008-04-09 中国科学院上海硅酸盐研究所 Complex self-curing material, method and application of bioactivity calcium phosphate/tricalcium silicate
WO2008095307A1 (en) * 2007-02-07 2008-08-14 Mcgill University Bioceramic implants having bioactive substance
WO2007062057A3 (en) * 2005-11-18 2009-04-23 Ceramatec Inc Porous, load-bearing, ceramic or metal implant
CN101690828A (en) * 2009-09-29 2010-04-07 西北工业大学 Preparation method of gradient porous bioceramic scaffold
CN104710188A (en) * 2015-03-02 2015-06-17 浙江大学 Porous calc silicate bioceramic material, preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1686576A (en) * 2005-05-08 2005-10-26 天津大学 Preparation method of beta-TCP/11A composite biological material
WO2007062057A3 (en) * 2005-11-18 2009-04-23 Ceramatec Inc Porous, load-bearing, ceramic or metal implant
WO2008095307A1 (en) * 2007-02-07 2008-08-14 Mcgill University Bioceramic implants having bioactive substance
CN101157045A (en) * 2007-10-26 2008-04-09 中国科学院上海硅酸盐研究所 Complex self-curing material, method and application of bioactivity calcium phosphate/tricalcium silicate
CN101690828A (en) * 2009-09-29 2010-04-07 西北工业大学 Preparation method of gradient porous bioceramic scaffold
CN104710188A (en) * 2015-03-02 2015-06-17 浙江大学 Porous calc silicate bioceramic material, preparation method and application

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Application publication date: 20160601