CN105770987A - 3D printing pulp of bone repair stent, bone repair stent and preparing method and application of bone repair stent - Google Patents
3D printing pulp of bone repair stent, bone repair stent and preparing method and application of bone repair stent Download PDFInfo
- Publication number
- CN105770987A CN105770987A CN201610225572.9A CN201610225572A CN105770987A CN 105770987 A CN105770987 A CN 105770987A CN 201610225572 A CN201610225572 A CN 201610225572A CN 105770987 A CN105770987 A CN 105770987A
- Authority
- CN
- China
- Prior art keywords
- slurry
- containing calcium
- polyvinyl alcohol
- bone repairing
- repairing support
- 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.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides 3D printing pulp of a bone repair stent. The 3D printing pulp of the bone repair stent is prepared from a polyvinyl alcohol aqueous solution with the mass-volume concentration of 4-8%, copper oxide and a biological ceramic material containing calcium and phosphate, wherein the mass volume ratio of the biological ceramic material containing calcium and phosphate to the polyvinyl alcohol aqueous solution is 2.5-3.5 g/mL, and the mass ratio of copper oxide to the biological ceramic material containing calcium and phosphate is (0.005-0.05):1. The 3D printing pulp is simple in formula and safe in ingredient, a dispersing agent or a defoaming agent or the like is not contained in the formula, and the obtained pulp is proper in viscosity and suitable for continuous extrusive 3D printing. The invention further provides a method for structuring the bone repair stent based on the 3D printing pulp and the obtained stent.
Description
Technical field
The present invention relates to biology medical material technical field, the 3D being specifically related to a kind of bone repairing support prints slurry
Material, bone repairing support and its preparation method and application.
Background technology
In recent years, the Cranial defect caused due to industrial accident, vehicle accident, orthopaedic disease etc. presents high
Sickness rate, China currently moves towards aging society, the orthopaedics degenerative disease relevant to aging population in addition
It is continuously increased, causes the demand to bone reparing biological material increasing.At present, bone tissue engineer technology
The shortcoming overcoming tradition Cranial defect implantation technique, provides a kind of new selection for clinical Bone Defect Repari treatment.
Wherein, the design of porous bone scaffold and structure, be one of key element determining bone tissue engineer repairing effect.
Traditional rack forming method (such as percolation, foaming, phase separation method, granule sintering process etc.) is certainly
Dynamicization degree is the highest, it is difficult to fully ensures the structure quality of bracket holes structure, and cannot enter microstructure
Row flexible design and accurately structure.In recent years, 3D prints as a kind of emerging advanced technologies, becomes
One of ideal chose preparing bone repairing support.Wherein (discussion below 3D prints 3D Plotting printing technique
Refer in particular to this technology) it is made by air extrusion pulp fiber, by the continuous stacked in multi-layers of fiber, build porous
Support.It can be by computer-aided design and most advanced and sophisticated printing device, and design and complete print have flexibly
The 3D solid of standby complicated microstructure, is widely used at present in terms of building Bone Defect Repari ceramics bracket.
But the premise that 3D prints bone repairing support is to prepare suitably to print slurry.At present, typical slurry is joined
Just by bioceramic powder body, thickening agent (such as methylcellulose, polyvinyl alcohol etc.), dispersant (such as polypropylene
Amide, polycarboxylic acids ammonium salt etc.), the structure such as flocculant (such as polymine) and defrother (such as n-octyl alcohol)
Become.The formula composition of existing printing slurry is complex, and the dispersant that relates to, defrother etc. are the most all
There is certain toxicity.
Additionally, tissue scaffold design important feature is to load with the functional somatomedin of slow release to improve
Repair function.But somatomedin itself exists, and the half-life is short, easy in inactivation, expensive and side effect risk
Etc. problem, carry the follow-up sterilizing of somatomedin support and storage is also a difficult problem.3D particularly with ceramic-like beats
Print support, forming process generally comprises high-temperature heating link.Somatomedin be typically only capable to after rack forming with
Ad hoc fashion is supported on rack surface, complex process, loaded down with trivial details.
Therefore, it is necessary to provide a kind of formula simple, nontoxic and can be suitably used for the printing slurry of 3D printing with system
Standby functional bone tissue engineering scaffold.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides that a kind of formula is simple, the Bone Defect Repari of safety non-toxic
The 3D of support prints slurry and the method building bone repairing support based on this slurry and the support obtained.
First aspect, the 3D that the invention provides a kind of bone repairing support prints slurry, described bone repairing support
3D to print slurry by mass body volume concentrations be the polyvinyl alcohol water solution of 4-8%, copper oxide and containing calcium
The bioceramic material composition of phosphorus, wherein, the described bioceramic material containing calcium phosphorus and described polyvinyl alcohol
The mass volume ratio of aqueous solution is 2.5-3.5g/mL, described copper oxide and the described bioceramic material containing calcium phosphorus
The mass ratio of material is 0.005-0.05:1.
Preferably, the described bioceramic material containing calcium phosphorus is hydroxyapatite, OCP, calcium phosphate
Or biphasic calcium phosphate, but it is not limited to this.
It is further preferred that the described bioceramic material containing calcium phosphorus is hydroxyapatite.
In the present invention, the described bioceramic material containing calcium phosphorus and the mass body of described polyvinyl alcohol water solution
Long-pending ratio is 2.5-3.5g/mL.The volume of polyvinyl alcohol (being abbreviated as PVA) aqueous solution improves, and slurry entirety becomes
Dilute, if PVA volume is too high, the fiber extruded cannot keep form；PVA volume reduces, and slurry entirety becomes
Thick, PVA volume is too low, and slurry cannot be extruded.
It is further preferred that the described bioceramic material containing calcium phosphorus and the matter of described polyvinyl alcohol water solution
Amount volume ratio is 2.5-3g/mL.That is, in the bioceramic material containing calcium phosphorus of every 30g, used
The volume of described polyvinyl alcohol water solution is 10-12mL.
Preferably, described copper oxide with the mass ratio of the described bioceramic material containing calcium phosphorus is
0.01-0.03:1。
Preferably, the particle diameter of the described bioceramic material containing calcium phosphorus is 10-15 μm.
Preferably, the 3D of described bone repairing support prints the viscosity of slurry is 200-300Pa s.
The 3D of the bone repairing support that the present invention provides prints slurry, and its formula is simple, composition safety, its formula
In without dispersant and defrother etc., contain only this kind of non-toxic excipients of polyvinyl alcohol, can be contained by regulation
Have the bioceramic material of calcium phosphorus and the quality volume proportion of polyvinyl alcohol to obtain slurry to be uniformly dispersed, be suitable for even
The 3D of continuous extrusion prints slurry.
Meanwhile, simultaneously added with copper oxide in the formula of described slurry, copper has been demonstrated to promote internal
Vascularization.Under the low-oxygen environment that Cranial defect causes, copper can promote cell synthesis hypoxia inducible factor (HIF-1)
With the expression of stimulating growth factor Ⅴ EGF, and copper ion can create favorable conditions for HIF-1 synthesis.Different
In traditional somatomedin, copper can directly incorporate the slurry of described bone repairing support by the mode such as being blended
In material, load capacity is relatively big and functional activity is not affected by printing technique.At the bone that described printing slurry is formed
In recovery support, it is expected to slow release copper ion to improve its Bone Defect Repari function.
Second aspect, the invention provides the preparation method of a kind of bone repairing support, comprises the following steps:
(1) preparation polyvinyl alcohol water solution；Weigh the bioceramic material containing calcium phosphorus and copper oxide, add
Entering described polyvinyl alcohol water solution, the mixture mix homogeneously that will obtain, the 3D obtaining bone repairing support prints
Slurry, it is water-soluble by the polyvinyl alcohol that mass body volume concentrations is 4-8% that the 3D of described bone repairing support prints slurry
Liquid, copper oxide and the composition of the bioceramic material containing calcium phosphorus, wherein, the described biological pottery containing calcium phosphorus
Ceramic material is 2.5-3.5g/mL with the mass volume ratio of described polyvinyl alcohol water solution, and described copper oxide is with described
The mass ratio of the bioceramic material containing calcium phosphorus is 0.005-0.05:1；
(2) described 3D printing slurry is carried out supersound process 10-20min at 50-80 DEG C, take out true afterwards
Sky, obtains the slurry after de-bubble；
(3) set 3D print parameters, by the slurry 3D printing shaping after described de-bubble, obtain Bone Defect Repari
Stent blank；
(4) by after described bone repairing support blank lyophilization, calcining, to remove polyvinyl alcohol, obtains bone and repaiies
Multiple support.
Preferably, the described bioceramic material containing calcium phosphorus is hydroxyapatite, OCP, calcium phosphate
Or biphasic calcium phosphate, but it is not limited to this.
It is further preferred that the described bioceramic material containing calcium phosphorus is hydroxyapatite.
Preferably, the described bioceramic material containing calcium phosphorus and the quality volume of described polyvinyl alcohol water solution
Ratio is 2.5-3g/mL.That is, in the bioceramic material containing calcium phosphorus of every 30g, used is described poly-
The volume of vinyl alcohol aqueous solution is 10-12mL.
Preferably, described copper oxide with the mass ratio of the described bioceramic material containing calcium phosphorus is
0.01-0.03:1。
Preferably, the particle diameter of the described bioceramic material containing calcium phosphorus is 10-15 μm.
Preferably, the 3D of described bone repairing support prints the viscosity of slurry is 200-300Pa s.
Preferably, described mixture mix homogeneously is to use high speed homogenization machine to carry out, described high speed homogenization machine
Homogenizing speed is 6000-8000rpm, and the time of described mixing is 15-20min.High speed homogenization machine is utilized to mix
Described mixture, can exempt the use of dispersant.
Preferably, described supersound process is to carry out 10-15min at 60 DEG C.Ultrasonic under heating slurry is made to become
Soft, it is easier to de-bubble.
Preferably, the time of described evacuation is 20min.The present invention uses ultrasonic and evacuation under heating
The mode combined can remove the bubble in described mixed slurry, can exempt the use of defrother, to the greatest extent may be used
Energy reduces the use of other reagent with certain toxicity, and the formula making described mixed slurry is simple, saving material,
Environmental Safety.
3D Plotting printing technique can carry out flexible modulation to the aperture of support, hole, connected ratio etc., system
Obtaining desired bone repairing support, in the embodiment of the present invention, described compound porous bone support is the solid of rule
(such as cuboid, square, cylinder etc., but being not limited to this) and other irregular three-dimensional porous knots
Structure body.It is preferably regular geometric body.
Preferably, described 3D print parameters includes that air pressure is 0.3-0.5MPa, fiber spacing 0.83mm, layer
High 0.2-0.4mm.When the viscosity of the slurry after described de-bubble is bigger, the air pressure needed for printing is relatively big, viscosity
Time less, the air pressure required for printing is less；Same slurry, when air pressure increases, the diameter of extrusion fiber is same
Shi Zeng great.
In the embodiment of the present invention, described bone repairing support is the described bioceramic material containing calcium phosphorus and oxidation
The three-dimensional porous rack that copper is constituted.The porosity of described bone repairing support is 50-70%.Described bone repairing support
The connected ratio of hole be 100%.
Preferably, the program of described calcining particularly as follows: be first raised to 400 DEG C with the speed of 1 DEG C/min from room temperature,
Insulation 1h；Then it is raised to 800 DEG C with the speed of 3 DEG C/min from room temperature, is incubated 2h.
In the preparation method of the described bone repairing support that second aspect present invention provides, use the poly-of specific proportioning
Vinyl alcohol aqueous solution, bioceramic material containing calcium phosphorus and copper oxide, can obtain slurry viscosity suitable,
The 3D being suitable for extrusion continuously prints slurry.Carry out disperseing by high speed homogenizer, ultrasonic combine with evacuation
Mode carry out de-bubble, the use of dispersant, defrother can be exempted, its formula is simple, composition safety.
The manufacture method of described bone repairing support is with low cost, relies on the height design of 3D printing technique, practicality
Stronger.
In the bone repairing support that described printing slurry is formed, it is compounded with the skeletonization that can promote stem cell and becomes
The copper of blood vessel differentiation.Being different from traditional somatomedin, copper directly can be melted by blending method
Entering in the slurry of described bone repairing support, load capacity is relatively big and functional activity is not affected by printing technique, reaches
To the purpose promoting Bone Defect Repari.
The third aspect, present invention also offers the preparation side of bone repairing support as described in respect of the second aspect of the invention
The bone repairing support that method obtains.
Fourth aspect, present invention also offers answering of a kind of bone repairing support as described in third aspect present invention
With.
Accompanying drawing explanation
Fig. 1 is the flow chart preparing bone repairing support that the embodiment of the present invention 1 provides, batch mixing (a), heating
Ultrasonic (b), evacuation (c), printing (d), lyophilization (e) and calcining (f).
Scanning electron microscope (SEM) photo of the bone repairing support that Fig. 2 provides for the embodiment of the present invention 1.
The SEM figure of the bone repairing support that Fig. 3 provides for the embodiment of the present invention 2.
The SEM figure of the bone repairing support that Fig. 4 provides for the embodiment of the present invention 3；
Fig. 5 is the comparison diagram of the cross section SEM of the bone repairing support of the embodiment of the present invention 1 and comparative example 1.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and reality
Execute example, the present invention is further elaborated.Only it should be pointed out that, specific embodiment described herein
Only in order to explain the present invention, it is not intended to limit the present invention.
Below in conjunction with specific embodiment, the invention will be further described.
Polyvinyl alcohol used in following embodiment is commercial goods, (1788 types, alcoholysis degree 87-89%, Ah
Latin)；Described hydroxyapatite is bought from Nanjing Ai Purui nano material company limited, medical grade.
Unless otherwise noted, the reagent that the embodiment of the present invention is used is all commercial goods.
Embodiment 1
Fig. 1 is the flow chart of a kind of method preparing bone repairing support, and in conjunction with Fig. 1, the embodiment of the present invention provides
A kind of method preparing bone repairing support, comprises the steps:
(1) preparation poly-vinyl alcohol solution: weigh 4g polyvinyl alcohol, join 100mL under agitation
Deionized water in；Continue stirring, and be gradually heated to 70 DEG C, be incubated 1h, form uniform solution；Stop
Only heating, continues stirring, after system naturally cools to room temperature, i.e. obtains poly-vinyl alcohol solution (4%, w/v)；
Weigh hydroxyapatite (i.e. HAP) powder body that 30g mean diameter is 12 μm and 0.3g, particle diameter are
The cupric oxide powder of 10 μm, is added step-wise in the poly-vinyl alcohol solution (4%, w/v) of 10ml, uses
High speed homogenization machine homogenizes speed to mix material 15min with 7000rpm, obtains uniform bone repairing support
3D print slurry, wherein, in described slurry, HAP:PVA=3 (w/v), CuO:HAP=0.3:30=0.01:1,
The viscosity of described slurry is about 250Pa s；
(2) slurry of mix homogeneously is loaded in the barrel of 3D printer, be placed in ultrasonic water bath pot,
Carry out ultrasonic 15min, afterwards evacuation 20min at 60 DEG C, obtain the slurry after de-bubble；
(3) barrel that will be equipped with de-bubble disposed slurry is installed on 3D printing device, sets 3D print parameters
(wherein, air pressure 0.3MPa, fiber spacing 0.83mm, floor height 0.32mm), by slurry printing shaping,
Obtain bone repairing support blank；
(4) by first for described bone repairing support blank freezing 12h at-20 DEG C, and at-80 DEG C of lyophilizing 48h,
Carry out calcining to remove polyvinyl alcohol by dried stent blank, obtain bone repairing support, be eventually stored in
In exsiccator；The program wherein calcined, particularly as follows: be first raised to 400 DEG C with the speed of 1 DEG C/min from room temperature, is protected
Temperature 1h；Then it is raised to 800 DEG C with the speed of 3 DEG C/min from room temperature, is incubated 2h.
The bone repairing support that the present embodiment 1 prepares is HAP and the three-dimensional porous rack (such as Fig. 2) of CuO composition,
The comprcssive strength of this support is 5MPa.
Embodiment 2:
A kind of method preparing bone repairing support, comprises the steps:
(1) preparation poly-vinyl alcohol solution 4%, w/v)；Weigh the hydroxyl that mean diameter is 10 μm of 30g
Apatite (i.e. HAP) powder body and the cupric oxide powder that 0.3g, particle diameter are 10 μm, be added step-wise to 12ml
Poly-vinyl alcohol solution (4%, w/v) in, use high speed homogenization machine with 6000rpm in the mixture that obtains
Homogenize speed mixing 15min, obtain uniform bone repairing support 3D print slurry, wherein, described slurry
In material, HAP:PVA=2.5 (w/v), CuO:HAP=0.3:30=0.01:1, the viscosity of described slurry is about 200
Pa·s；
(2) slurry of mix homogeneously is loaded in the barrel of 3D printer, be placed in ultrasonic device, at 50 DEG C
Under carry out ultrasonic 15min, afterwards evacuation 20min, obtain the slurry after de-bubble；
(3) barrel that will be equipped with de-bubble disposed slurry is installed on 3D printing device, sets 3D print parameters
(wherein, air pressure 0.3MPa, fiber spacing 0.83mm, floor height 0.28mm), by slurry printing shaping,
Obtain bone repairing support blank；
(4) by first for described bone repairing support blank freezing 12h at-20 DEG C, and at-80 DEG C of lyophilizing 48h,
Carry out calcining to remove polyvinyl alcohol by dried stent blank, obtain bone repairing support, be eventually stored in
In exsiccator；The program wherein calcined, particularly as follows: be first raised to 400 DEG C with the speed of 1 DEG C/min from room temperature, is protected
Temperature 1h；Then it is raised to 800 DEG C with the speed of 3 DEG C/min from room temperature, is incubated 2h.
The bone repairing support that the present embodiment 2 prepares is HAP and the three-dimensional porous rack (Fig. 3) of CuO composition.
Compared with (Fig. 2) in embodiment 1, owing to the mass volume ratio of PVA solution is slightly dropped by hydroxyapatite
Low, the pressure needed for slurry prints slightly reduces；Floor height reduces simultaneously, to make up slurry in print procedure
Shrinkage degree.
Embodiment 3:
A kind of method preparing bone repairing support, comprises the steps:
(1) preparation poly-vinyl alcohol solution (8%, w/v)；Weigh the hydroxyapatite of a diameter of 12 μm of 30g
(i.e. HAP) powder body and the cupric oxide powder of 0.9g, be added step-wise to 10ml poly-vinyl alcohol solution (8%,
W/v), in, the mixture obtained use high speed homogenization machine mix 15min with the speed that homogenizes of 8000rpm,
The 3D obtaining uniform bone repairing support prints slurry, wherein, HAP:PVA=3 (w/v) in described slurry,
CuO:HAP=0.9:30=0.03:1, the viscosity of described slurry is about 300Pa s；
(2) slurry of mix homogeneously is loaded in the barrel of 3D printer, be placed in ultrasonic device, at 60 DEG C
Under carry out ultrasonic 15min, afterwards evacuation 20min, obtain the slurry after de-bubble；
(3) barrel that will be equipped with de-bubble disposed slurry is installed on 3D printing device, sets 3D print parameters
(wherein, air pressure 0.5MPa, fiber spacing 0.83mm, floor height 0.32mm), by slurry printing shaping,
Obtain bone repairing support blank；
(4) by first for described bone repairing support blank freezing 12h at-20 DEG C, and at-80 DEG C of lyophilizing 48h,
Carry out calcining to remove polyvinyl alcohol by dried stent blank, obtain bone repairing support, be eventually stored in
In exsiccator；The program wherein calcined, particularly as follows: be first raised to 400 DEG C with the speed of 1 DEG C/min from room temperature, is protected
Temperature 1h；Then it is raised to 800 DEG C with the speed of 3 DEG C/min from room temperature, is incubated 2h.
The bone repairing support that the present embodiment prepares is HAP and the three-dimensional porous rack (Fig. 4) of CuO composition,
Compared with embodiment 1, CuO content and PVA concentration in the present embodiment increase, and slurry is corresponding
Batch mixing speed and extrusion pressure improve the most accordingly.
The described bone repairing support that embodiment of the present invention 1-3 prepares is cuboid, and shape is the most as in Figure 2-4.
Wherein porosity is 100%, and the connected ratio of hole is 50-70%.
Embodiment 4:
A kind of method preparing bone repairing support, comprises the steps:
(1) preparation poly-vinyl alcohol solution (6%, w/v)；Weigh the hydroxyl that mean diameter is 15 μm of 36g
Base apatite (i.e. HAP) powder body and the cupric oxide powder of 0.3g, be added step-wise to the polyvinyl alcohol of 12ml
In solution (6%, w/v), high speed homogenization machine is used to homogenize speed with 6300rpm in the mixture obtained
Mixing 20min, the 3D obtaining uniform bone repairing support prints slurry, wherein, in described slurry,
HAP:PVA=3 (w/v), CuO:HAP=0.3:36=0.008:1, the viscosity of described slurry is about 210Pa s；
(2) slurry of mix homogeneously is loaded in the barrel of 3D printer, be placed in ultrasonic device, at 70 DEG C
Under carry out ultrasonic 10min, afterwards evacuation 20min, obtain the slurry after de-bubble；
(3) barrel that will be equipped with de-bubble disposed slurry is installed on 3D printing device, sets 3D print parameters
(wherein, air pressure 0.3MPa, fiber spacing 0.83mm, floor height 0.35mm), by slurry printing shaping,
Obtain bone repairing support blank；
(4) by first for described bone repairing support blank freezing 12h at-20 DEG C, and at-80 DEG C of lyophilizing 48h,
Carry out calcining to remove polyvinyl alcohol by dried stent blank, obtain bone repairing support, be eventually stored in
In exsiccator；The program wherein calcined, particularly as follows: be first raised to 400 DEG C with the speed of 1 DEG C/min from room temperature, is protected
Temperature 1h；Then it is raised to 800 DEG C with the speed of 3 DEG C/min from room temperature, is incubated 2h；Described bone repairing support is
The three-dimensional porous rack that HAP and CuO is constituted.
For absolutely proving effective effect of the present invention, be also directed to embodiment 1 be provided with its contrast enforcement 1, its with
The difference of enforcement one is, after the slurry being uniformly mixed, is directly loadable into the barrel of 3D printer
In, processing without de-bubble and to be mounted directly to print on 3D printing device, remaining operation is with embodiment 1.
The SEM in the cross section of the bone repairing support that comparative example 1 and the embodiment of the present invention 1 prepare schemes such as Fig. 5
Shown in, wherein (A) is comparative example 1, and (B) is the embodiment of the present invention 1.Compared with Example 1,
Owing to processing without de-bubble, there is more irregular hole (Fig. 5 in the bone internal stent that comparative example 1 obtains
A in around corner), this mechanical property that can largely effect on bone support and stability.It should be noted that
Big black holes in the middle of A, B of Fig. 5 is the hole of porous support itself, is the pulp fiber observed of cross sectional view
Between hole.
For those skilled in the art, under the premise without departing from the principles of the invention, also
Can make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. the 3D of a bone repairing support prints slurry, it is characterised in that the 3D of described bone repairing support
Printing slurry by mass body volume concentrations is the polyvinyl alcohol water solution of 4-8%, copper oxide and the life containing calcium phosphorus
Thing ceramic material forms, wherein, and the described bioceramic material containing calcium phosphorus and described polyvinyl alcohol water solution
Mass volume ratio be 2.5-3.5g/mL, the matter of described copper oxide and the described bioceramic material containing calcium phosphorus
Amount ratio is 0.005-0.05:1.
2. 3D as claimed in claim 1 prints slurry, it is characterised in that the described biology containing calcium phosphorus
Ceramic material is hydroxyapatite, OCP, calcium phosphate or biphasic calcium phosphate, and particle diameter is 10-15 μm.
3. 3D as claimed in claim 1 prints slurry, it is characterised in that described copper oxide contains with described
The mass ratio having the bioceramic material of calcium phosphorus is 0.01-0.03:1.
4. 3D as claimed in claim 1 prints slurry, it is characterised in that the 3D of described bone repairing support
The viscosity printing slurry is 200-300Pa s.
5. the preparation method of a bone repairing support, it is characterised in that comprise the steps:
(1) preparation polyvinyl alcohol water solution；Weigh the bioceramic material containing calcium phosphorus and copper oxide, add
Entering described polyvinyl alcohol water solution, the mixture mix homogeneously that will obtain, the 3D obtaining bone repairing support prints
Slurry, it is water-soluble by the polyvinyl alcohol that mass body volume concentrations is 4-8% that the 3D of described bone repairing support prints slurry
Liquid, copper oxide and the composition of the bioceramic material containing calcium phosphorus, wherein, the described biological pottery containing calcium phosphorus
Ceramic material is 2.5-3.5g/mL with the mass volume ratio of described polyvinyl alcohol water solution, and described copper oxide is with described
The mass ratio of the bioceramic material containing calcium phosphorus is 0.005-0.05:1；
(2) described 3D printing slurry is carried out supersound process 10-20min at 50-70 DEG C, take out true afterwards
Sky, obtains the slurry after de-bubble；
(3) set 3D print parameters, by the slurry 3D printing shaping after described de-bubble, obtain Bone Defect Repari
Stent blank；
(4) by after described bone repairing support blank lyophilization, calcining, to remove polyvinyl alcohol, obtains bone and repaiies
Multiple support.
6. preparation method as claimed in claim 5, it is characterised in that the described bioceramic containing calcium phosphorus
Material is 2.5-3g/mL with the mass volume ratio of described polyvinyl alcohol water solution.
7. preparation method as claimed in claim 5, it is characterised in that the described mixture mixing that will obtain
Being uniformly to use high speed homogenization machine to carry out, the speed that homogenizes of described high speed homogenization machine is 6000-8000rpm, institute
The time stating mixing is 15-20min.
8. preparation method as claimed in claim 5, it is characterised in that described supersound process is to enter at 60 DEG C
Row 10-15min.
9. the bone repairing support that the preparation method as described in any one of claim 5-8 obtains.
10. the application of a bone repairing support as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610225572.9A CN105770987B (en) | 2016-04-12 | 2016-04-12 | A kind of 3D printing slurry of bone repairing support, bone repairing support and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610225572.9A CN105770987B (en) | 2016-04-12 | 2016-04-12 | A kind of 3D printing slurry of bone repairing support, bone repairing support and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105770987A true CN105770987A (en) | 2016-07-20 |
| CN105770987B CN105770987B (en) | 2018-12-28 |
Family
ID=56396341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610225572.9A Active CN105770987B (en) | 2016-04-12 | 2016-04-12 | A kind of 3D printing slurry of bone repairing support, bone repairing support and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105770987B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106421900A (en) * | 2016-09-30 | 2017-02-22 | 深圳先进技术研究院 | 3D printing paste of tissue repair bracket, tissue repair bracket as well as preparation method and application of tissue repair bracket |
| CN106606802A (en) * | 2016-12-06 | 2017-05-03 | 广州邦菲医疗器械科技有限公司 | 3D-printed bone repair scaffold containing multistage channels and manufacturing method thereof |
| CN106668934A (en) * | 2016-12-15 | 2017-05-17 | 中山职业技术学院 | Calcium-phosphate-based 3D printing material for biomedicine and preparation method thereof |
| CN106726010A (en) * | 2016-12-14 | 2017-05-31 | 深圳先进技术研究院 | Three-dimensional bone repairing support with very low power and its preparation method and application |
| CN106822990A (en) * | 2017-03-06 | 2017-06-13 | 吴建国 | The artificial eye socket bone preparation method of perforated sectional |
| CN107137774A (en) * | 2017-06-06 | 2017-09-08 | 上海理工大学 | A kind of fibroin albumen with three-dimensional structure/hydroxyapatite compound rest and preparation method thereof |
| CN107185034A (en) * | 2017-05-04 | 2017-09-22 | 中国科学院上海硅酸盐研究所 | Bioceramic scaffold and its production and use is repaired in osteochondral defect integration |
| CN109053185A (en) * | 2018-09-08 | 2018-12-21 | 佛山市森昂生物科技有限公司 | A kind of preparation method of biological active ceramic material |
| CN109133907A (en) * | 2018-08-16 | 2019-01-04 | 迈海新型材料科技（固安）有限公司 | A kind of artificial bone and preparation method thereof comprising hydroxyapatite crystal whisker and biphase calcium phosphor |
| CN112043870A (en) * | 2020-08-18 | 2020-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of 3D-printed polyvinyl alcohol/calcium phosphate drug-loaded bone repair scaffold, product and application thereof |
| CN114014647A (en) * | 2021-10-21 | 2022-02-08 | 华南理工大学 | Zinc silicate composite tricalcium phosphate ceramic support and preparation method and application thereof |
| CN114195509A (en) * | 2021-11-08 | 2022-03-18 | 西北工业大学 | Direct-writing 3D printing universal ink modified by nonionic surfactant and preparation and printing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060230984A1 (en) * | 2002-09-25 | 2006-10-19 | Z Corporation | Three dimensional printing material system and method |
| CN103721292A (en) * | 2012-10-10 | 2014-04-16 | 中国科学院上海硅酸盐研究所 | Novel multifunctional mesoporous glass bracket with biological activity as well as preparation method and purpose thereof |
| US20150097385A1 (en) * | 2013-06-12 | 2015-04-09 | Ford Global Technologies, Llc | Bonded and Rotatable Vehicle Sensor Assembly |
| CN105233346A (en) * | 2015-10-27 | 2016-01-13 | 深圳大学 | Porous biological support slurry, three-dimensional porous biological support and preparation method of support |
-
2016
- 2016-04-12 CN CN201610225572.9A patent/CN105770987B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060230984A1 (en) * | 2002-09-25 | 2006-10-19 | Z Corporation | Three dimensional printing material system and method |
| CN103721292A (en) * | 2012-10-10 | 2014-04-16 | 中国科学院上海硅酸盐研究所 | Novel multifunctional mesoporous glass bracket with biological activity as well as preparation method and purpose thereof |
| US20150097385A1 (en) * | 2013-06-12 | 2015-04-09 | Ford Global Technologies, Llc | Bonded and Rotatable Vehicle Sensor Assembly |
| CN105233346A (en) * | 2015-10-27 | 2016-01-13 | 深圳大学 | Porous biological support slurry, three-dimensional porous biological support and preparation method of support |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106421900B (en) * | 2016-09-30 | 2019-04-26 | 深圳先进技术研究院 | The 3D printing slurry of tissue recovery support, tissue recovery support and its preparation method and application |
| CN106421900A (en) * | 2016-09-30 | 2017-02-22 | 深圳先进技术研究院 | 3D printing paste of tissue repair bracket, tissue repair bracket as well as preparation method and application of tissue repair bracket |
| CN106606802A (en) * | 2016-12-06 | 2017-05-03 | 广州邦菲医疗器械科技有限公司 | 3D-printed bone repair scaffold containing multistage channels and manufacturing method thereof |
| CN106726010B (en) * | 2016-12-14 | 2018-07-24 | 深圳先进技术研究院 | Three-dimensional bone repairing support with very low power and its preparation method and application |
| CN106726010A (en) * | 2016-12-14 | 2017-05-31 | 深圳先进技术研究院 | Three-dimensional bone repairing support with very low power and its preparation method and application |
| CN106668934A (en) * | 2016-12-15 | 2017-05-17 | 中山职业技术学院 | Calcium-phosphate-based 3D printing material for biomedicine and preparation method thereof |
| CN106822990A (en) * | 2017-03-06 | 2017-06-13 | 吴建国 | The artificial eye socket bone preparation method of perforated sectional |
| CN107185034A (en) * | 2017-05-04 | 2017-09-22 | 中国科学院上海硅酸盐研究所 | Bioceramic scaffold and its production and use is repaired in osteochondral defect integration |
| CN107185034B (en) * | 2017-05-04 | 2020-07-14 | 中国科学院上海硅酸盐研究所 | Bone-cartilage defect integrated repair biological ceramic scaffold and preparation method and application thereof |
| CN107137774A (en) * | 2017-06-06 | 2017-09-08 | 上海理工大学 | A kind of fibroin albumen with three-dimensional structure/hydroxyapatite compound rest and preparation method thereof |
| CN109133907A (en) * | 2018-08-16 | 2019-01-04 | 迈海新型材料科技（固安）有限公司 | A kind of artificial bone and preparation method thereof comprising hydroxyapatite crystal whisker and biphase calcium phosphor |
| CN109053185A (en) * | 2018-09-08 | 2018-12-21 | 佛山市森昂生物科技有限公司 | A kind of preparation method of biological active ceramic material |
| CN112043870A (en) * | 2020-08-18 | 2020-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of 3D-printed polyvinyl alcohol/calcium phosphate drug-loaded bone repair scaffold, product and application thereof |
| CN114014647A (en) * | 2021-10-21 | 2022-02-08 | 华南理工大学 | Zinc silicate composite tricalcium phosphate ceramic support and preparation method and application thereof |
| CN114195509A (en) * | 2021-11-08 | 2022-03-18 | 西北工业大学 | Direct-writing 3D printing universal ink modified by nonionic surfactant and preparation and printing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105770987B (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105770987A (en) | 3D printing pulp of bone repair stent, bone repair stent and preparing method and application of bone repair stent | |
| EP1960097B1 (en) | Ultrastable particle-stabilized foams and emulsions | |
| Shum et al. | Double emulsion droplets as microreactors for synthesis of mesoporous hydroxyapatite | |
| US7514024B2 (en) | Method for producing a porous sintered body of calcium phosphate-based ceramic | |
| US20110136653A1 (en) | Method for the production of a porous, ceramic surface layer | |
| US20100167020A1 (en) | Casting Process | |
| DE69914207T2 (en) | FOAM CERAMICS | |
| JP4540969B2 (en) | Calcium phosphate ceramic porous body and method for producing the same | |
| CN107311640A (en) | Composition and application method with open pores ceramics are prepared for 3D printing | |
| CN106726010B (en) | Three-dimensional bone repairing support with very low power and its preparation method and application | |
| JP5422784B1 (en) | Method for producing calcium phosphate porous body, and calcium phosphate porous body obtained by the production method | |
| CN104357955B (en) | Preparation method of one-dimensional hollow porous structure calcium titanate nanofiber | |
| CN105381505A (en) | 3D printing preparation method of bond defect repair stent | |
| Zhang et al. | Aqueous processing of hydroxyapatite | |
| JP4699902B2 (en) | Calcium phosphate ceramic porous body and method for producing the same | |
| CN109133972A (en) | A kind of porous bioceramic scaffold and preparation method thereof | |
| JPH08133858A (en) | Mixed raw materials for producing porous ceramic sintered product | |
| JP7016610B2 (en) | Porous ceramics manufacturing method and porous ceramics | |
| ES2755421T3 (en) | New manufacturing process in a single stage of alveolar biomaterials | |
| EP1293220A1 (en) | Porous calcium phosphate ceramics for in vivo use | |
| WO2013035690A1 (en) | Porous body and method for producing porous body | |
| JP5793045B2 (en) | Method for producing ceramic porous body | |
| DE102012211390B4 (en) | SYNTHETIC BONE REPLACEMENT MATERIAL AND METHOD FOR THE PRODUCTION THEREOF | |
| AT504168B1 (en) | METHOD FOR PRODUCING AN IN PARTICULAR POROUS CERAMIC FORM BODY AND FORM BODY MANUFACTURED THEREWITH | |
| CN112876281B (en) | Preparation method and application of biological ceramic support with hollow microsphere surface micro-nano structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |