CN105770987B - A kind of 3D printing slurry of bone repairing support, bone repairing support and its preparation method and application - Google Patents
A kind of 3D printing slurry of bone repairing support, bone repairing support and its preparation method and application Download PDFInfo
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- CN105770987B CN105770987B CN201610225572.9A CN201610225572A CN105770987B CN 105770987 B CN105770987 B CN 105770987B CN 201610225572 A CN201610225572 A CN 201610225572A CN 105770987 B CN105770987 B CN 105770987B
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Abstract
The present invention provides a kind of 3D printing slurries of bone repairing support, the 3D printing slurry of the bone repairing support is that the polyvinyl alcohol water solution of 4-8%, copper oxide and bioceramic material containing calcium phosphorus form by mass-volume concentration, wherein, the mass volume ratio of the bioceramic material containing calcium phosphorus and the polyvinyl alcohol water solution is 2.5-3.5g/mL, and the mass ratio of the copper oxide and the bioceramic material containing calcium phosphorus is 0.005-0.05:1.The 3D printing formula of size is simple, ingredient is safe, and without dispersing agent and defrother etc. in formula, the viscosity for obtaining slurry is suitable, is suitble to the 3D printing continuously squeezed out.The present invention also provides the method based on 3D printing slurry building bone repairing support and obtained brackets.
Description
Technical field
The present invention relates to biomedical material technologies, and in particular to a kind of 3D printing slurry, the bone of bone repairing support
Recovery support and its preparation method and application.
Background technique
In recent years, the bone defect as caused by industrial accident, traffic accident, orthopaedic disease etc. shows high disease incidence,
In addition China just moves towards aging society at present, and orthopaedics degenerative disease relevant to elderly population is continuously increased, and causes to bone
The demand of reparing biological material is increasing.Currently, bone tissue engineer technology overcomes lacking for traditional bone defect implantation technique
Point provides a kind of new selection for clinical Bone Defect Repari treatment.Wherein, the design and building of porous bone scaffold is to determine bone group
One of the key element of weaver's journey repairing effect.
The degree of automation is or not traditional rack forming method (such as percolation, foaming, phase separation method, particle sintering process)
It is high, it is difficult to sufficiently to ensure the building quality of bracket pore structure, and flexible design and accurate building can not be carried out to microstructure.
In recent years, 3D printing becomes as a kind of emerging advanced technologies and prepares one of ideal chose of bone repairing support.Wherein
3D Plotting printing technique (technology is refered in particular in following discussion 3D printing) is to squeeze out pulp fiber by air, passes through fiber
Continuous stacked in multi-layers constructs porous support.It can flexibly conceive by the printing device of CAD and tip
Have the 3D solid of complicated microstructure with complete print, is widely used in terms of constructing Bone Defect Repari ceramics bracket at present.
But the premise of 3D printing bone repairing support is to prepare suitable printing slurry.Currently, typical formula of size is by giving birth to
Object ceramic powder, thickener (such as methylcellulose, polyvinyl alcohol), dispersing agent (such as polyacrylamide, polycarboxylic acids ammonium salt),
Flocculant (such as polyethyleneimine) and defrother (such as n-octyl alcohol) are constituted.The formula composition of existing printing slurry is more multiple
Miscellaneous, dispersing agent, the defrother etc. being related to often have certain toxicity.
In addition, an important feature of tissue scaffold design is load and is sustained functional growth factor to improve reparation function
Energy.However growth factor the problems such as there are half-life short, easy in inactivation, expensive and side effect risks itself, carry growth factor
The subsequent sterilizing of bracket and storage are also problem.Particularly with the 3D printing bracket of ceramic-like, forming process generally comprises high temperature
Heated link.Growth factor is typically only capable to be supported on rack surface in a specific way after rack forming, complex process, cumbersome.
Therefore, it is necessary to provide a kind of printing slurry that is simple, nontoxic and can be suitably used for 3D printing is formulated to prepare function
The bone tissue engineering scaffold of property.
Summary of the invention
Simple, safe and non-toxic bone repairing support is formulated in order to solve the above-mentioned technical problems, the present invention provides a kind of
3D printing slurry and the bracket for constructing the method for bone repairing support based on the slurry and obtaining.
In a first aspect, the present invention provides a kind of 3D printing slurry of bone repairing support, the 3D of the bone repairing support is beaten
Printing paste material is the polyvinyl alcohol water solution of 4-8%, copper oxide and bioceramic material containing calcium phosphorus by mass-volume concentration
Composition, wherein the mass volume ratio of the bioceramic material containing calcium phosphorus and the polyvinyl alcohol water solution is 2.5-
The mass ratio of 3.5g/mL, the copper oxide and the bioceramic material containing calcium phosphorus is 0.005-0.05:1.
Preferably, the bioceramic material containing calcium phosphorus is hydroxyapatite, calcium octahate phosphate, calcium phosphate or two-phase phosphorus
Sour calcium, but not limited to this.
It is further preferred that the bioceramic material containing calcium phosphorus is hydroxyapatite.
In the present invention, the mass volume ratio of the bioceramic material containing calcium phosphorus and the polyvinyl alcohol water solution is
2.5-3.5g/mL.The volume of polyvinyl alcohol (being abbreviated as PVA) aqueous solution improves, and slurry is integrally thinning, if PVA volume is excessively high
The fiber of extrusion cannot keep form；PVA volume reduces, and slurry entirety retrogradation, PVA volume is too low, and slurry can not squeeze out.
It is further preferred that the quality volume of the bioceramic material containing calcium phosphorus and the polyvinyl alcohol water solution
Than for 2.5-3g/mL.That is, in the bioceramic material containing calcium phosphorus of every 30g, the used polyvinyl alcohol water solution
Volume is 10-12mL.
Preferably, the mass ratio of the copper oxide and the bioceramic material containing calcium phosphorus is 0.01-0.03:1.
Preferably, the partial size of the bioceramic material containing calcium phosphorus is 10-15 μm.
Preferably, the viscosity of the 3D printing slurry of the bone repairing support is 200-300Pas.
The 3D printing slurry of bone repairing support provided by the invention is formulated simple, ingredient safety, is free of and divides in formula
Powder and defrother etc. only contain a kind of this non-toxic excipients of polyvinyl alcohol, can be by adjusting the bioceramic material containing calcium phosphorus
The quality volume proportion of material and polyvinyl alcohol obtains slurry and is uniformly dispersed, is suitble to the 3D printing slurry continuously squeezed out.
Meanwhile simultaneously added with copper oxide in the formula of the slurry, copper has been demonstrated to can promote body vessel.
Under low-oxygen environment caused by bone defect, copper can promote cell synthesis hypoxia inducible factor (HIF-1) with the stimulating growth factor
The expression of VEGF, and copper ion can create favorable conditions for HIF-1 synthesis.Different from traditional growth factor, copper can be with
It is directly incorporated in the slurry of the bone repairing support by modes such as blendings, load capacity is larger and functional activity is not by printing technology
Influence.In the bone repairing support that the printing slurry is formed, sustained release copper ion is expected to improve its Bone Defect Repari function.
Second aspect, the present invention provides a kind of preparation methods of bone repairing support, comprising the following steps:
(1) polyvinyl alcohol water solution is prepared；Bioceramic material and copper oxide containing calcium phosphorus are weighed, is added described poly-
Obtained mixture is uniformly mixed by vinyl alcohol aqueous solution, obtains the 3D printing slurry of bone repairing support, the bone repairing support
3D printing slurry by mass-volume concentration be that the polyvinyl alcohol water solution of 4-8%, copper oxide and biology containing calcium phosphorus are made pottery
Ceramic material composition, wherein the mass volume ratio of the bioceramic material containing calcium phosphorus and the polyvinyl alcohol water solution is
The mass ratio of 2.5-3.5g/mL, the copper oxide and the bioceramic material containing calcium phosphorus is 0.005-0.05:1；
(2) the 3D printing slurry is subjected at 50-80 DEG C ultrasonic treatment 10-20min, vacuumizes, is removed later
Slurry after bubble；
(3) 3D printing parameter is set, the slurry 3D printing after the de-bubble is formed, bone repairing support blank is obtained；
(4) it by after bone repairing support blank freeze-drying, calcines to remove polyvinyl alcohol, obtains bone repairing support.
Preferably, the bioceramic material containing calcium phosphorus is hydroxyapatite, calcium octahate phosphate, calcium phosphate or two-phase phosphorus
Sour calcium, but not limited to this.
It is further preferred that the bioceramic material containing calcium phosphorus is hydroxyapatite.
Preferably, the mass volume ratio of the bioceramic material containing calcium phosphorus and the polyvinyl alcohol water solution is
2.5-3g/mL.That is, in the bioceramic material containing calcium phosphorus of every 30g, the volume of the used polyvinyl alcohol water solution
For 10-12mL.
Preferably, the mass ratio of the copper oxide and the bioceramic material containing calcium phosphorus is 0.01-0.03:1.
Preferably, the partial size of the bioceramic material containing calcium phosphorus is 10-15 μm.
Preferably, the viscosity of the 3D printing slurry of the bone repairing support is 200-300Pas.
Preferably, the mixture, which is uniformly mixed, is carried out using high speed homogenization machine, and the high speed homogenization machine homogenizes speed
Degree is 6000-8000rpm, and the mixed time is 15-20min.Mix the mixture using high speed homogenization machine, can in order to avoid
Except the use of dispersing agent.
Preferably, the ultrasonic treatment is that 10-15min is carried out at 60 DEG C.Heating lower ultrasound can make slurry soften, and more hold
Easy de-bubble.
Preferably, the time vacuumized is 20min.It is combined using heating lower ultrasound with vacuumizing in the present invention
Mode can remove the bubble in the mixed slurry, can exempt the use of defrother, reduce as far as possible with certain toxicity
The use of other reagents keeps the formula of the mixed slurry simple, saves material, Environmental Safety.
3D Plotting printing technique can aperture, hole, connected ratio to bracket etc. carry out flexible modulation, the phase is made
The bone repairing support of prestige, in the embodiment of the present invention, the compound porous bone bracket is solid (such as cuboid, pros of rule
Body, cylindrical body etc., but not limited to this) and other irregular three-dimensional porous structure bodies.Preferably regular geometric body.
Preferably, it is 0.3-0.5MPa, fiber spacing 0.83mm, the high 0.2- of layer that the 3D printing parameter, which includes air pressure,
0.4mm.When the viscosity of slurry after the de-bubble is larger, it is larger to print required air pressure, when viscosity is smaller, required for printing
Air pressure it is smaller；Same slurry squeezes out the diameter of fiber while increasing when air pressure increases.
In the embodiment of the present invention, the bone repairing support is that the bioceramic material containing calcium phosphorus and copper oxide are constituted
Three-dimensional porous rack.The porosity of the bone repairing support is 50-70%.The connected ratio of the hole of the bone repairing support is
100%.
Preferably, the program of the calcining specifically: be first raised to 400 DEG C from room temperature with the rate of 1 DEG C/min, keep the temperature 1h；
Then 800 DEG C are raised to from room temperature with the rate of 3 DEG C/min, keep the temperature 2h.
In the preparation method for the bone repairing support that second aspect of the present invention provides, using the polyvinyl alcohol of specific proportion
Aqueous solution, bioceramic material and copper oxide containing calcium phosphorus, available slurry viscosity is suitable, is suitble to the 3D continuously squeezed out
Print slurry.Dispersed high speed homogenizer, ultrasound de-bubble is carried out by way of vacuumizing and combining, dispersion can be exempted
Agent, the use of defrother, formula is simple, ingredient is safe.The manufacturing method of the bone repairing support is low in cost, and 3D is relied on to beat
The height design of print technology, practicability are stronger.
In the bone repairing support that the printing slurry is formed, it is compounded with the skeletonization that can promote stem cell and at blood vessel point
The copper of change.Different from traditional growth factor, copper can directly incorporate the bone repairing support by blending method
Slurry in, load capacity is larger and functional activity is not influenced by printing technology, achieve the purpose that promote Bone Defect Repari.
The third aspect, the present invention also provides the preparation methods of bone repairing support as described in respect of the second aspect of the invention to obtain
Bone repairing support.
Fourth aspect, the present invention also provides a kind of applications of bone repairing support as described in the third aspect of the present invention.
Detailed description of the invention
Fig. 1 is the flow chart for preparing bone repairing support that the embodiment of the present invention 1 provides, and mixing (a) heats ultrasonic (b), takes out
Vacuum (c), printing (d), freeze-drying (e) and calcining (f).
Fig. 2 is scanning electron microscope (SEM) photo for the bone repairing support that the embodiment of the present invention 1 provides.
Fig. 3 is the SEM figure for the bone repairing support that the embodiment of the present invention 2 provides.
Fig. 4 is the SEM figure for the bone repairing support that the embodiment of the present invention 3 provides；
Fig. 5 is the comparison diagram of the section SEM of the bone repairing support of the embodiment of the present invention 1 and comparative example 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be pointed out that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The present invention is further explained in the light of specific embodiments.
Polyvinyl alcohol as used in the following examples is commercial goods, (1788 types, alcoholysis degree 87-89%, Aladdin)；Institute
Hydroxyapatite purchase is stated from Nanjing Ai Purui nano material Co., Ltd, medical grade.
Unless otherwise noted, reagent used by the embodiment of the present invention is all commercial goods.
Embodiment 1
Fig. 1 is a kind of flow chart of method for preparing bone repairing support, and in conjunction with Fig. 1, the embodiment of the invention provides one kind
The method for preparing bone repairing support, includes the following steps:
(1) it prepares poly-vinyl alcohol solution: weighing 4g polyvinyl alcohol, be added to the deionized water of 100mL under agitation
In；Continue to stir, and be gradually heated to 70 DEG C, keeps the temperature 1h, form uniform solution；Stop heating, continue to stir, certainly to system
To get to poly-vinyl alcohol solution (4%, w/v) after being so cooled to room temperature；
Weigh hydroxyapatite (i.e. HAP) powder and 0.3g, the copper oxide that partial size is 10 μm that 30g average grain diameter is 12 μm
Powder is added step-wise in the poly-vinyl alcohol solution (4%, w/v) of 10ml, high speed homogenization machine is used to homogenize speed with 7000rpm
Degree carrys out mixing material 15min, obtains the 3D printing slurry of uniform bone repairing support, wherein in the slurry, HAP:PVA=3
(w/v), CuO:HAP=0.3:30=0.01:1, the viscosity of the slurry are about 250Pas；
(2) uniformly mixed slurry is fitted into the barrel of 3D printer, is placed in ultrasonic water bath pot, is carried out at 60 DEG C
Ultrasonic 15min, vacuumizes 20min later, the slurry after obtaining de-bubble；
(3) barrel equipped with slurry after de-bubble is installed in 3D printing equipment, sets (wherein, the air pressure of 3D printing parameter
0.3MPa, fiber spacing 0.83mm, the high 0.32mm of layer), by slurry printing shaping, obtain bone repairing support blank；
(4) the bone repairing support blank is first freezed into 12h at -20 DEG C, and in -80 DEG C of freeze-drying 48h, after drying
Stent blank is calcined to remove polyvinyl alcohol, and bone repairing support is obtained, and is eventually stored in drier；The journey wherein calcined
Sequence specifically: be first raised to 400 DEG C from room temperature with the rate of 1 DEG C/min, keep the temperature 1h；Then with the rate of 3 DEG C/min from room temperature liter
To 800 DEG C, 2h is kept the temperature.
Bone repairing support made from the present embodiment 1 is the three-dimensional porous rack (such as Fig. 2) that HAP and CuO is constituted, the bracket
Compression strength is 5MPa.
Embodiment 2:
A method of bone repairing support is prepared, is included the following steps:
(1) poly-vinyl alcohol solution 4%, w/v are prepared)；The hydroxyapatite that the average grain diameter for weighing 30g is 10 μm is (i.e.
HAP) powder and 0.3g, the cupric oxide powder that partial size is 10 μm, are added step-wise to the poly-vinyl alcohol solution (4%, w/v) of 12ml
In, it uses high speed homogenization machine to mix 15min with the speed that homogenizes of 6000rpm in obtained mixture, obtains uniform Bone Defect Repari
The 3D printing slurry of bracket, wherein in the slurry, HAP:PVA=2.5 (w/v), CuO:HAP=0.3:30=0.01:1, institute
The viscosity for stating slurry is about 200Pas；
(2) uniformly mixed slurry is fitted into the barrel of 3D printer, is placed in ultrasonic device, is surpassed at 50 DEG C
Sound 15min, vacuumizes 20min later, the slurry after obtaining de-bubble；
(3) barrel equipped with slurry after de-bubble is installed in 3D printing equipment, sets (wherein, the air pressure of 3D printing parameter
0.3MPa, fiber spacing 0.83mm, the high 0.28mm of layer), by slurry printing shaping, obtain bone repairing support blank；
(4) the bone repairing support blank is first freezed into 12h at -20 DEG C, and in -80 DEG C of freeze-drying 48h, after drying
Stent blank is calcined to remove polyvinyl alcohol, and bone repairing support is obtained, and is eventually stored in drier；The journey wherein calcined
Sequence specifically: be first raised to 400 DEG C from room temperature with the rate of 1 DEG C/min, keep the temperature 1h；Then with the rate of 3 DEG C/min from room temperature liter
To 800 DEG C, 2h is kept the temperature.
Bone repairing support made from the present embodiment 2 is the three-dimensional porous rack (Fig. 3) that HAP and CuO is constituted.With embodiment 1
In (Fig. 2) compare, since hydroxyapatite slightly reduces the mass volume ratio of PVA solution, pressure needed for slurry printing is omited
There is reduction；Layer height reduces simultaneously, to make up shrinkage degree of the slurry in print procedure.
Embodiment 3:
A method of bone repairing support is prepared, is included the following steps:
(1) poly-vinyl alcohol solution (8%, w/v) is prepared；Weigh hydroxyapatite (i.e. HAP) powder that 30g diameter is 12 μm
It with the cupric oxide powder of 0.9g, is added step-wise in the poly-vinyl alcohol solution (8%, w/v) of 10ml, obtained mixture is used
High speed homogenization machine homogenizes speed mixing 15min with 8000rpm's, obtains the 3D printing slurry of uniform bone repairing support, wherein
HAP:PVA=3 (w/v), CuO:HAP=0.9:30=0.03:1 in the slurry, the viscosity of the slurry are about 300Pas；
(2) uniformly mixed slurry is fitted into the barrel of 3D printer, is placed in ultrasonic device, is surpassed at 60 DEG C
Sound 15min, vacuumizes 20min later, the slurry after obtaining de-bubble；
(3) barrel equipped with slurry after de-bubble is installed in 3D printing equipment, sets (wherein, the air pressure of 3D printing parameter
0.5MPa, fiber spacing 0.83mm, the high 0.32mm of layer), by slurry printing shaping, obtain bone repairing support blank；
(4) the bone repairing support blank is first freezed into 12h at -20 DEG C, and in -80 DEG C of freeze-drying 48h, after drying
Stent blank is calcined to remove polyvinyl alcohol, and bone repairing support is obtained, and is eventually stored in drier；The journey wherein calcined
Sequence specifically: be first raised to 400 DEG C from room temperature with the rate of 1 DEG C/min, keep the temperature 1h；Then with the rate of 3 DEG C/min from room temperature liter
To 800 DEG C, 2h is kept the temperature.
Bone repairing support made from the present embodiment is the three-dimensional porous rack (Fig. 4) that HAP and CuO is constituted, in embodiment 1
It compares, the CuO content and PVA concentration in the present embodiment increase, and the corresponding mixing rate of slurry and extrusion pressure are also corresponding
It improves.
The bone repairing support made from 1-3 of the embodiment of the present invention is cuboid, and shape difference is as in Figure 2-4.Wherein
Porosity is 100%, and the connected ratio of hole is 50-70%.
Embodiment 4:
A method of bone repairing support is prepared, is included the following steps:
(1) poly-vinyl alcohol solution (6%, w/v) is prepared；The hydroxyapatite that the average grain diameter for weighing 36g is 15 μm is (i.e.
HAP) the cupric oxide powder of powder and 0.3g is added step-wise in the poly-vinyl alcohol solution (6%, w/v) of 12ml, mixed by what is obtained
Closing object uses high speed homogenization machine to homogenize speed mixing 20min with 6300rpm, obtains the 3D printing slurry of uniform bone repairing support
Material, wherein in the slurry, HAP:PVA=3 (w/v), CuO:HAP=0.3:36=0.008:1, the viscosity of the slurry is about
For 210Pas；
(2) uniformly mixed slurry is fitted into the barrel of 3D printer, is placed in ultrasonic device, is surpassed at 70 DEG C
Sound 10min, vacuumizes 20min later, the slurry after obtaining de-bubble；
(3) barrel equipped with slurry after de-bubble is installed in 3D printing equipment, sets (wherein, the air pressure of 3D printing parameter
0.3MPa, fiber spacing 0.83mm, the high 0.35mm of layer), by slurry printing shaping, obtain bone repairing support blank；
(4) the bone repairing support blank is first freezed into 12h at -20 DEG C, and in -80 DEG C of freeze-drying 48h, after drying
Stent blank is calcined to remove polyvinyl alcohol, and bone repairing support is obtained, and is eventually stored in drier；The journey wherein calcined
Sequence specifically: be first raised to 400 DEG C from room temperature with the rate of 1 DEG C/min, keep the temperature 1h；Then with the rate of 3 DEG C/min from room temperature liter
To 800 DEG C, 2h is kept the temperature；The bone repairing support is the three-dimensional porous rack that HAP and CuO is constituted.
To absolutely prove effective effect of the invention, its comparison is provided with also directed to embodiment 1 and implements 1, with implementation one
The difference is that being directly loadable into the barrel of 3D printer after obtaining uniformly mixed slurry, without de-bubble processing
It is mounted directly in 3D printing equipment and is printed, remaining operation is the same as embodiment 1.
The SEM in the section of bone repairing support made from comparative example 1 and the embodiment of the present invention 1 schemes as shown in figure 5, wherein
It (A) is comparative example 1, (B) is the embodiment of the present invention 1.Compared with Example 1, due to handling without de-bubble, comparison is implemented
For the bone internal stent that example 1 obtains there are more irregular hole (surrounding quadrangle in the A of Fig. 5), this can largely effect on bone bracket
Mechanical property and stability.It is worth noting that, the big black holes among A, B of Fig. 5 is the hole of porous support itself, it is section view
The hole between pulp fiber that figure is observed.
For those skilled in the art, without departing from the principle of the present invention, it can also do
Several improvements and modifications out, these modifications and embellishments are also considered to be within the scope of the present invention.
Claims (8)
1. a kind of 3D printing slurry of bone repairing support, which is characterized in that the 3D printing slurry of the bone repairing support is by quality
Polyvinyl alcohol water solution, copper oxide and the bioceramic material composition containing calcium phosphorus that volumetric concentration is 4-8%, wherein institute
The mass volume ratio for stating the bioceramic material containing calcium phosphorus and the polyvinyl alcohol water solution is 2.5-3.5g/mL, the oxygen
The mass ratio for changing copper and the bioceramic material containing calcium phosphorus is 0.005-0.05:1；The 3D printing of the bone repairing support
The viscosity of slurry is 200-300Pas.
2. 3D printing slurry as described in claim 1, which is characterized in that the bioceramic material containing calcium phosphorus is hydroxyl
Apatite, calcium octahate phosphate, tricalcium phosphate or biphasic calcium phosphate, partial size are 10-15 μm.
3. 3D printing slurry as described in claim 1, which is characterized in that the copper oxide and the biology containing calcium phosphorus are made pottery
The mass ratio of ceramic material is 0.01-0.03:1.
4. a kind of preparation method of bone repairing support, which comprises the steps of:
(1) polyvinyl alcohol water solution is prepared；Bioceramic material and copper oxide containing calcium phosphorus are weighed, the polyethylene is added
Obtained mixture is uniformly mixed by alcohol solution, obtains the 3D printing slurry of bone repairing support, the 3D of the bone repairing support
It is the polyvinyl alcohol water solution of 4-8%, copper oxide and bioceramic material containing calcium phosphorus that slurry, which is printed, by mass-volume concentration
Material composition, wherein the mass volume ratio of the bioceramic material containing calcium phosphorus and the polyvinyl alcohol water solution is 2.5-
The mass ratio of 3.5g/mL, the copper oxide and the bioceramic material containing calcium phosphorus is 0.005-0.05:1；The bone is repaired
The viscosity of the 3D printing slurry of multiple bracket is 200-300Pas；
(2) the 3D printing slurry is subjected at 50-70 DEG C ultrasonic treatment 10-20min, vacuumized later, after obtaining de-bubble
Slurry；
(3) 3D printing parameter is set, the slurry 3D printing after the de-bubble is formed, bone repairing support blank is obtained；
(4) it by after bone repairing support blank freeze-drying, calcines to remove polyvinyl alcohol, obtains bone repairing support.
5. preparation method as claimed in claim 4, which is characterized in that the bioceramic material containing calcium phosphorus gathers with described
The mass volume ratio of vinyl alcohol aqueous solution is 2.5-3g/mL.
6. preparation method as claimed in claim 4, which is characterized in that described be uniformly mixed obtained mixture is using height
Fast homogenization machine carries out, and the speed that homogenizes of the high speed homogenization machine is 6000-8000rpm, and the mixed time is 15-20min.
7. preparation method as claimed in claim 4, which is characterized in that the ultrasonic treatment is in 60 DEG C of progress 10-15min.
8. a kind of bone repairing support obtained such as the described in any item preparation methods of claim 4-7.
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| 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 |
| 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 |
| CN106668934B (en) * | 2016-12-15 | 2019-10-25 | 中山职业技术学院 | A kind of biomedical calcium orthophosphate base 3D printing material 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 |
| 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 |
| CN114014647B (en) * | 2021-10-21 | 2022-12-16 | 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 |
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